Resist underlayer film forming composition containing silicon having ester group

ABSTRACT

A resist underlayer film forming composition for lithography for a resist underlayer film usable as a hardmask. A resist underlayer film forming composition for lithography, including: as a silane, a hydrolyzable silane, a hydrolysis product thereof, or a hydrolysis-condensation product thereof, wherein the hydrolyzable silane includes a hydrolyzable silane of Formula (1) or a hydrolyzable silane containing a combination of a hydrolyzable silane of Formula (1) with a hydrolyzable silane of Formula (2), and a content of the hydrolyzable silane of Formula (1) or the hydrolyzable silane containing a combination of a hydrolyzable silane of Formula (1) with a hydrolyzable silane of Formula (2) in all silanes is less than 50% by mole, 
       R 1   a R 2   b Si(R 3 ) 4−(a+b)   Formula (1)
 
       R 4   a1 R 5   b1 Si(R 6 ) 4−(a1+b1)   Formula (2)

TECHNICAL FIELD

The present invention relates to a composition for forming an underlayerfilm between a substrate and a resist (for example, a photoresist and anEUV resist) that are used in the production of semiconductor devices.More in detail, the present invention relates to a resist underlayerfilm forming composition for lithography for forming an underlayer filmused for an underlayer of a photoresist in a lithography process of theproduction of semiconductor devices. In addition, the present inventionrelates to a forming method of a resist pattern using the underlayerfilm forming composition.

BACKGROUND ART

Conventionally, in the production of semiconductor devices, fineprocessing by lithography using a photoresist has been performed. Thefine processing is a processing method for forming fine convexo-concaveshapes corresponding to the following pattern on the surface of asubstrate by: forming a thin film of a photoresist on a semiconductorsubstrate such as a silicon wafer; irradiating the resultant thin filmwith active rays such as ultraviolet rays through a mask pattern inwhich a pattern of a semiconductor device is depicted; developing thethin film; and subjecting the substrate to etching processing using theresultant photoresist pattern as a protecting film.

However, recently, high integration of semiconductor devices hasprogressed and the adopted active rays tend to have a shorterwavelength, such as an ArF excimer laser (193 nm), replacing a KrFexcimer laser (248 nm). Following such a tendency, the influence ofreflection of active rays on a semiconductor substrate has become alarge issue.

As an underlayer film between the semiconductor substrate and thephotoresist, the use of a film known as a hardmask containing a metalelement such as silicon or titanium has been performed. In this case,the resist and the hardmask have components largely differ from eachother, so that the removal rates of the resist and the hardmask by dryetching largely depend on the type of a gas used for dry etching. Byappropriately selecting the type of a gas, the hardmask can be removedby dry etching without a large decrease in the film thickness of thephotoresist.

As described above, in the production of semiconductor devices in recentyears, for achieving various effects such as the reflection preventingeffect, a resist underlayer film has become disposed between thesemiconductor substrate and the photoresist. The studies of acomposition for a resist underlayer film have been performed; however,due to the diversity of characteristics required for the composition andso on, development of a novel material for the resist underlayer film isdesired.

For example, a resist underlayer film containing a polysiloxane using asilane having an ester bond is described (see Patent Document 1, PatentDocument 2, and Patent Document 3).

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: Japanese Patent Application Publication No.2007-226170 (JP 2007-226170 A)

Patent Document 2: Japanese Patent Application Publication No.2004-310019 (JP 2004-310019 A)

Patent Document 3: International Publication No. WO 2006057782 Pamphlet

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

It is an object of the present invention to provide a resist underlayerfilm forming composition for lithography usable in the production ofsemiconductor devices. More in detail, it is an object of the presentinvention to provide a resist underlayer film forming composition forlithography for forming a resist underlayer film usable as a hardmask.In addition, it is an object of the present invention to provide aresist underlayer film forming composition for lithography for forming aresist underlayer film usable as an anti-reflective coating.Furthermore, it is an object of the present invention to provide aresist underlayer film for lithography causing no intermixing with aresist and having a dry etching rate higher than that of the resist, anda resist underlayer film forming composition for forming the underlayerfilm.

In particular, it is an object of the present invention to provide aresist underlayer film forming composition for forming a resistunderlayer film capable of forming an excellent resist pattern shapewhen a resist as an upper layer of the resist underlayer film is exposedto light and the resist is developed with an alkaline developer or anorganic solvent, and capable of transferring a rectangular resistpattern to an underlayer of the resist underlayer film by dry etching ina subsequent process.

Means for Solving the Problem

The present invention relates to, according to a first aspect, a resistunderlayer film forming composition for lithography, comprising: as asilane, a hydrolyzable silane, a hydrolysis product thereof, or ahydrolysis-condensation product thereof, in which the hydrolyzablesilane includes a hydrolyzable silane of Formula (1) or a hydrolyzablesilane containing a combination of a hydrolyzable silane of Formula (1)with a hydrolyzable silane of Formula (2), and a content of thehydrolyzable silane of Formula (1) or the hydrolyzable silane containinga combination of a hydrolyzable silane of Formula (1) with ahydrolyzable silane of Formula (2) in all silanes is less than 50% bymole,

R¹ _(a)R² _(b)Si(R³)_(4−(a+b))  Formula (1)

[in Formula (1), R¹ is a monovalent organic group containing a group ofFormula (1-1), Formula (1-2), Formula (1-3), Formula (1-4), or Formula(1-5):

(in Formula (1-1), Formula (1-2), Formula (1-3), Formula (1-4), andFormula (1-5), each of T¹, T⁴, and T⁷ is an alkylene group, a cyclicalkylene group, an alkenylene group, an arylene group, a sulfur atom, anoxygen atom, an oxycarbonyl group, an amido group, a secondary aminogroup, or a combination of these groups and atoms; T² is an alkyl group;each of T³ and T⁵ is an aliphatic ring or an aromatic ring; each of T⁶and T⁸ is a lactone ring; and n is an integer of 1 or 2) and is bondedto a silicon atom through a Si—C bond; R² is an alkyl group, an arylgroup, a halogenated alkyl group, a halogenated aryl group, an alkenylgroup, or an organic group having an epoxy group, an acryloyl group, amethacryloyl group, a mercapto group, an amino group, or a cyano group,and is bonded to a silicon atom through a Si—C bond; R³ is an alkoxygroup, an acyloxy group, or a halogen group; and a is an integer of 1, bis an integer of 0 or 1, and a+b is an integer of 1 or 2],

R⁴ _(a1)R⁵ _(b1)Si(R⁶)_(4−(a1+b1))  Formula (2)

[in Formula (2), R⁴ is a monovalent organic group containing a group ofFormula (2-1), Formula (2-2), or Formula (2-3):

and is bonded to a silicon atom through a Si—C bond; R⁵ is an alkylgroup, an aryl group, a halogenated alkyl group, a halogenated arylgroup, an alkenyl group, or an organic group having an epoxy group, anacryloyl group, a methacryloyl group, a mercapto group, an amino group,or a cyano group, and is bonded to a silicon atom through a Si—C bond;R⁶ is an alkoxy group, an acyloxy group, or a halogen group; and a₁ isan integer of 1, b₁ is an integer of 0 or 1, and a₁ b₁ is an integer of1 or 2];

according to a second aspect, the resist underlayer film formingcomposition according to the first aspect, in which a content of thehydrolyzable silane of Formula (1) or the hydrolyzable silane containinga combination of a hydrolyzable silane of Formula (1) with ahydrolyzable silane of Formula (2) in all silanes is 5 to 45% by mole;

according to a third aspect, the resist underlayer film formingcomposition according to the first aspect or the second aspect, in whicha hydrolyzable silane of Formula (2) is a hydrolyzable silane in whichR⁴ is an organic group containing a group of Formula (2-1), ahydrolyzable silane in which R⁴ is an organic group containing a groupof Formula (2-2), a hydrolyzable silane in which R⁴ is an organic groupcontaining a group of Formula (2-3), or a mixture of these hydrolyzablesilanes;

according to a fourth aspect, the resist underlayer film formingcomposition according to any one of the first aspect to the thirdaspect, in which a hydrolyzable silane containing a combination of ahydrolyzable silane of Formula (1) with a hydrolyzable silane of Formula(2) contains a hydrolyzable silane of Formula (1) and a hydrolyzablesilane of Formula (2) in a molar ratio of 1:0.01 to 10;

according to a fifth aspect, the resist underlayer film formingcomposition for lithography according to any one of the first aspect tothe fourth aspect, in which the hydrolyzable silane contains ahydrolyzable silane of Formula (1) or a hydrolyzable silane containing acombination of a hydrolyzable silane of Formula (1) with a hydrolyzablesilane of Formula (2), and another hydrolyzable silane, and the otherhydrolyzable silane is at least one organic silicon compound selectedfrom the group consisting of a compound of Formula (3):

R⁷ _(a2)Si(R⁸)_(4−a2)  Formula (3)

(in Formula (3), R⁷ is an alkyl group, an aryl group, a halogenatedalkyl group, a halogenated aryl group, an alkenyl group, or an organicgroup having an epoxy group, an acryloyl group, a methacryloyl group, amercapto group, or a cyano group, and is bonded to a silicon atomthrough a Si—C bond; R⁸ is an alkoxy group, an acyloxy group, or ahalogen group; and a₂ is an integer of 0 to 3) and a compound of Formula(4):

[R⁹ _(c)Si(R¹⁰)_(3−c)]Y_(b2)  Formula (4)

(in Formula (4), R⁹ is an alkyl group and is bonded to a silicon atomthrough a Si—C bond; R¹⁰ is an alkoxy group, an acyloxy group, or ahalogen group; Y is an alkylene group or an arylene group; b₂ is aninteger of 0 or 1; and c is an integer of 0 or 1);

according to a sixth aspect, a resist underlayer film formingcomposition, comprising: a hydrolysis product of a hydrolyzable silaneof Formula (1) as described in any one of the first aspect to the fourthaspect, a hydrolyzable silane of Formula (2) as described in any one ofthe first aspect to the fourth aspect, and a hydrolyzable silane ofFormula (3) as described in the fifth aspect, as a polymer;

according to a seventh aspect, the resist underlayer film formingcomposition according to any one of the first aspect to the sixthaspect, further comprising an acid as a hydrolysis catalyst;

-   -   according to an eighth aspect, the resist underlayer film        forming composition according to any one of the first aspect to        the seventh aspect, further comprising water;

according to a ninth aspect, a resist underlayer film obtained byapplying the resist underlayer film forming composition as described inany one of the first aspect to the eighth aspect onto a semiconductorsubstrate, and baking the composition;

according to a tenth aspect, a method for producing a semiconductordevice, the method comprising: applying the resist underlayer filmforming composition as described in any one of the first aspect to theeighth aspect onto a semiconductor substrate and baking the compositionto form a resist underlayer film; applying a composition for a resistonto the underlayer film to form a resist film; exposing the resist filmto light; developing the resist after the exposure to obtain a resistpattern; etching the resist underlayer film using the resist pattern;and processing the semiconductor substrate using the patterned resistand the patterned resist underlayer film; and

according to an eleventh aspect, a method for producing a semiconductordevice, the method comprising: forming an organic underlayer film on asemiconductor substrate; applying the resist underlayer film formingcomposition as described in any one of the first aspect to the eighthaspect onto the organic underlayer film and baking the composition toform a resist underlayer film; applying a composition for a resist ontothe resist underlayer film to form a resist film; exposing the resistfilm to light; developing the resist after the exposure to obtain aresist pattern; etching the resist underlayer film using the resistpattern; etching the organic underlayer film using the patterned resistunderlayer film; and processing the semiconductor substrate using thepatterned organic underlayer film.

Effects of the Invention

In the present invention, the substrate is coated in such an order thatthe substrate is coated with the resist underlayer film (containing aninorganic silicon-based compound) formed from the composition of thepresent invention either with or without an organic underlayer filminterposed therebetween, and then the resist underlayer film is coatedwith a resist film (an organic resist film).

Then, the resist underlayer film of the present invention functions as ahardmask, and a hydrolyzable group such as an alkoxy group, an acyloxygroup, and a halogen group in the structure of a hydrolyzable silanecompound of Formula (1) is hydrolyzed or partially hydrolyzed and then,the resultant silanol group is subjected to a condensation reaction toform a polymer having a polysiloxane structure. The polyorganosiloxanestructure (intermediate film) is effective as a hardmask for etching anorganic underlayer film existing as an underlayer of the intermediatefilm or for processing (etching) the substrate. That is, theintermediate film has satisfactory dry etching resistance during thesubstrate processing or against an oxygen-based dry etching gas foretching the organic underlayer film.

These bonding moieties contained in the polyorganosiloxane structurehave a carbon-nitrogen bond or a carbon-oxygen bond, so that the bondingmoieties have a dry etching rate by using a halogen-based gas higherthan that of a carbon-carbon bond and then, are effective upontransferring a pattern of the upper layer resist to the resistunderlayer film.

Thus, a resist underlayer film formed from the composition of thepresent invention can enhance the dry etching rate of the resistunderlayer film relative to the upper layer resist and possesses dryetching resistance of the resist underlayer film during the substrateprocessing or the like.

Accordingly, by using as a hardmask, a polyorganosiloxane produced froma hydrolyzable silane compound of Formula (1) having an ester group(that is, ester bond) or a hydrolyzable silane containing a combinationof the hydrolyzable silane compound with a hydrolyzable silane compoundof Formula (2) having an amido group (that is, amide bond), a sulfonegroup (that is, sulfonyl bond), or a phenyl group, where thesehydrolyzable silane compounds are contained in the composition of thepresent invention, when the upper layer resist is exposed to light andis developed with an alkaline developer or an organic solvent, anexcellent resist pattern shape can be formed and a rectangular resistpattern can be transferred to an underlayer by dry etching in asubsequent process.

MODES FOR CARRYING OUT THE INVENTION

The present invention provides a resist underlayer film formingcomposition for lithography characterized by containing as a silane, ahydrolyzable silane, a hydrolysis product thereof, ahydrolysis-condensation product thereof, characterized in that thesilane includes a hydrolyzable silane of Formula (1) or a hydrolyzablesilane containing a combination of a hydrolyzable silane of Formula (1)with a hydrolyzable silane of Formula (2), and a content of ahydrolyzable silane of Formula (1) or a hydrolyzable silane containing acombination of a hydrolyzable silane of Formula (1) with a hydrolyzablesilane of Formula (2) in all silanes is less than 50% by mole.

The hydrolyzable silane of Formula (1) or the hydrolyzable silanecontaining a combination of a hydrolyzable silane of Formula (1) with ahydrolyzable silane of Formula (2) may be used in a content in a rangeof less than 50% by mole, or 5 to 45% by mole, or 5 to 40% by mole, or 5to 35% by mole, or 5 to 30% by mole, or 10 to 20% by mole in allsilanes.

The resist underlayer film forming composition of the present inventioncontains a hydrolyzable silane of Formula (1) or a hydrolyzable silanecontaining a combination of a hydrolyzable silane of Formula (1) with ahydrolyzable silane of Formula (2), a hydrolysis product thereof, or ahydrolysis-condensation product thereof, and a solvent. In addition, thecomposition may contain as optional components, an acid, water, analcohol, a curing catalyst, an acid generator, other organic polymers, alight absorptive compound, a surfactant, or the like.

The solid content in the resist underlayer film forming composition ofthe present invention is, for example, 0.1 to 50% by mass, 0.1 to 30% bymass, or 0.1 to 25% by mass. Here, the solid content is a componentremaining after removing a solvent component from all components of theresist underlayer film forming composition.

The content of a hydrolyzable silane, a hydrolysis product thereof, or ahydrolysis-condensation product thereof in the solid content is 20% bymass or more, for example, 50 to 100% by mass, 60 to 100% by mass, or 70to 100% by mass.

Then, the hydrolyzable silane, the hydrolysis product thereof, and thehydrolysis-condensation product thereof may also be used as a mixturethereof. The hydrolyzable silane is hydrolyzed and the resultanthydrolysis product thereof is subjected to condensation to produce thehydrolysis-condensation product thereof which may be used in thecomposition. When the hydrolysis-condensation product is obtained, apartially-hydrolyzed product produced by incomplete hydrolysis and asilane compound are mixed in the hydrolysis-condensation product andsuch a mixture may also be used in the composition. The condensationproduct is a polymer having a polysiloxane structure. The polysiloxanecontains a hydrolysis product of a hydrolyzable silane of Formula (1) ora hydrolyzable silane containing a combination of a hydrolyzable silaneof Formula (1) with a hydrolyzable silane of Formula (2). To ahydrolysis-condensation product (polysiloxane) of a hydrolysis productof a hydrolyzable silane of Formula (1) or a hydrolyzable silanecontaining a combination of a hydrolyzable silane of Formula (1) with ahydrolyzable silane of Formula (2), a hydrolyzable silane of Formula (1)or a hydrolyzable silane of Formula (1) and a hydrolyzable silane ofFormula (2) may be added.

To a hydrolysis-condensation product (polysiloxane) not containing ahydrolysis product of a hydrolyzable silane of Formula (1) or ahydrolyzable silane containing a combination of a hydrolyzable silane ofFormula (1) with a hydrolyzable silane of Formula (2), a hydrolyzablesilane of Formula (1) or a hydrolyzable silane containing a combinationof a hydrolyzable silane of Formula (1) with a hydrolyzable silane ofFormula (2) may be added.

In a hydrolyzable silane of Formula (1) used in the present invention,R¹ is a monovalent organic group containing a group of Formula (1-1),Formula (1-2), Formula (1-3), Formula (1-4), or Formula (1-5) and isbonded to a silicon atom through a Si—C bond. R² is an alkyl group, anaryl group, a halogenated alkyl group, a halogenated aryl group, analkenyl group, or an organic group having an epoxy group, an acryloylgroup, a methacryloyl group, a mercapto group, an amino group, or acyano group, and is bonded to a silicon atom through a Si—C bond. R³ isan alkoxy group, an acyloxy group, or a halogen group. The index a is aninteger of 1, b is an integer of 0 or 1, and a+b is an integer of 1 or2. In Formula (1-1), Formula (1-2), Formula (1-3), Formula (1-4), andFormula (1-5), each of T¹, T⁴, and T⁷ is an alkylene group, a cyclicalkylene group, an alkenylene group, an arylene group, a sulfur atom, anoxygen atom, an oxycarbonyl group, an amido group, a secondary aminogroup, or a combination of these groups and atoms; T² is an alkyl group;each of T³ and T⁵ is an aliphatic ring or an aromatic ring; and each ofT⁶ and T⁸ is a lactone ring. In Formula (1-1), n is an integer of 1 or2.

The hydrolyzable silane of Formula (1) may be a hydrolyzable silanecontaining an organic group containing a group of Formula (1-1), ahydrolyzable silane containing an organic group containing a group ofFormula (1-2), a hydrolyzable silane containing an organic groupcontaining a group of Formula (1-3), a hydrolyzable silane containing anorganic group containing a group of Formula (1-4), a hydrolyzable silanecontaining an organic group containing a group of Formula (1-5), or amixture of these hydrolyzable silanes.

A lactone ring of T⁶ and T⁸ is a ring in which a carbon atom of onecarbonyl group and an oxygen atom of one ester exist on the ring.

In a hydrolyzable silane of Formula (2) used in the present invention,R⁴ is a monovalent organic group containing a group of Formula (2-1),Formula (2-2), or Formula (2-3) and is bonded to a silicon atom througha Si—C bond. R⁵ is an alkyl group, an aryl group, a halogenated alkylgroup, a halogenated aryl group, an alkenyl group, or an organic grouphaving an epoxy group, an acryloyl group, a methacryloyl group, amercapto group, an amino group, or a cyano group, and is bonded to asilicon atom through a Si—C bond. R⁶ is an alkoxy group, an acyloxygroup, or a halogen group. a₁ is an integer of 1 and b₁ is an integer of0 or 1, and a₁+b₁ is an integer of 1 or 2.

The hydrolyzable silane of Formula (2) may be a hydrolyzable silanecontaining an organic group containing a group of Formula (2-1), ahydrolyzable silane containing an organic group containing a group ofFormula (2-2), a hydrolyzable silane containing an organic groupcontaining a group of Formula (2-3), or a mixture of these hydrolyzablesilanes.

The resist underlayer film forming composition for lithography of thepresent invention may contain a hydrolyzable silane of Formula (1) and ahydrolyzable silane of Formula (2) in a molar ratio of 1:0.01 to 10, or1:0.1 to 10, or 1:0.1 to 5.

The alkyl group is a linear or branched alkyl group having a carbon atomnumber of 1 to 10 and examples of the alkyl group include a methylgroup, an ethyl group, an n-propyl group, an isopropyl group, an n-butylgroup, an isobutyl group, a sec-butyl group, a tert-butyl group, ann-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 4-methyl-n-pentylgroup, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group.

As the alkyl group, a cyclic alkyl group may also be used and examplesof a C₁₋₁₀ cyclic alkyl group include a cyclopropyl group, a cyclobutylgroup, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, acyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutylgroup, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a2-ethyl-cyclopropyl group, a cyclohexyl group, a 1-methyl-cyclopentylgroup, a 2-methyl-cyclopentyl group, a 3-methyl-cyclopentyl group, a1-ethyl-cyclobutyl group, a 2-ethyl-cyclobutyl group, a3-ethyl-cyclobutyl group, a 1,2-dimethyl-cyclobutyl group, a1,3-dimethyl-cyclobutyl group, a 2,2-dimethyl-cyclobutyl group, a2,3-dimethyl-cyclobutyl group, a 2,4-dimethyl-cyclobutyl group, a3,3-dimethyl-cyclobutyl group, a 1-n-propyl-cyclopropyl group, a2-n-propyl-cyclopropyl group, a 1-isopropyl-cyclopropyl group, a2-isopropyl-cyclopropyl group, a 1,2,2-trimethyl-cyclopropyl group, a1,2,3-trimethyl-cyclopropyl group, a 2,2,3-trimethyl-cyclopropyl group,a 1-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-1-methyl-cyclopropylgroup, a 2-ethyl-2-methyl-cyclopropyl group, and a2-ethyl-3-methyl-cyclopropyl group.

Examples of the alkylene group include alkylene groups derived from theabove alkyl groups. Examples of the alkylene group include a methylenegroup derived from a methyl group, an ethylene group derived from anethyl group, a propylene group derived from a propyl group.

Examples of the alkenyl group include C₂₋₁₀ alkenyl groups such as anethenyl group, a 1-propenyl group, a 2-propenyl group, a1-methyl-1-ethenyl group, a 1-butenyl group, a 2-butenyl group, a3-butenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenylgroup, a 1-ethyl ethenyl group, a 1-methyl-1-propenyl group, a1-methyl-2-propenyl group, a 1-pentenyl group, a 2-pentenyl group, a3-pentenyl group, a 4-pentenyl group, a 1-n-propyl ethenyl group, a1-methyl-1-butenyl group, a 1-methyl-2-butenyl group, a1-methyl-3-butenyl group, a 2-ethyl-2-propenyl group, a2-methyl-1-butenyl group, a 2-methyl-2-butenyl group, a2-methyl-3-butenyl group, a 3-methyl-1-butenyl group, a3-methyl-2-butenyl group, a 3-methyl-3-butenyl group, a1,1-dimethyl-2-propenyl group, a 1-isopropyl ethenyl group, a1,2-dimethyl-1-propenyl group, a 1,2-dimethyl-2-propenyl group, a1-cyclopentenyl group, a 2-cyclopentenyl group, a 3-cyclopentenyl group,a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenylgroup, a 5-hexenyl group, a 1-methyl-1-pentenyl group, a1-methyl-2-pentenyl group, a 1-methyl-3-pentenyl group, a1-methyl-4-pentenyl group, a 1-n-butyl ethenyl group, a2-methyl-1-pentenyl group, a 2-methyl-2-pentenyl group, a2-methyl-3-pentenyl group, a 2-methyl-4-pentenyl group, a2-n-propyl-2-propenyl group, a 3-methyl-1-pentenyl group, a3-methyl-2-pentenyl group, a 3-methyl-3-pentenyl group, a3-methyl-4-pentenyl group, a 3-ethyl-3-butenyl group, a4-methyl-1-pentenyl group, a 4-methyl-2-pentenyl group, a4-methyl-3-pentenyl group, a 4-methyl-4-pentenyl group, a1,1-dimethyl-2-butenyl group, a 1,1-dimethyl-3-butenyl group, a1,2-dimethyl-1-butenyl group, a 1,2-dimethyl-2-butenyl group, a1,2-dimethyl-3-butenyl group, a 1-methyl-2-ethyl-2-propenyl group, a1-sec-butyl ethenyl group, a 1,3-dimethyl-1-butenyl group, a1,3-dimethyl-2-butenyl group, a 1,3-dimethyl-3-butenyl group, a1-isobutyl ethenyl group, a 2,2-dimethyl-3-butenyl group, a2,3-dimethyl-1-butenyl group, a 2,3-dimethyl-2-butenyl group, a2,3-dimethyl-3-butenyl group, a 2-isopropyl-2-propenyl group, a3,3-dimethyl-1-butenyl group, a 1-ethyl-1-butenyl group, a1-ethyl-2-butenyl group, a 1-ethyl-3-butenyl group, a1-n-propyl-1-propenyl group, a 1-n-propyl-2-propenyl group, a2-ethyl-1-butenyl group, a 2-ethyl-2-butenyl group, a 2-ethyl-3-butenylgroup, a 1,1,2-trimethyl-2-propenyl group, a 1-tert-butyl ethenyl group,a 1-methyl-1-ethyl-2-propenyl group, a 1-ethyl-2-methyl-1-propenylgroup, a 1-ethyl-2-methyl-2-propenyl group, a 1-isopropyl-1-propenylgroup, a 1-isopropyl-2-propenyl group, a 1-methyl-2-cyclopentenyl group,a 1-methyl-3-cyclopentenyl group, a 2-methyl-1-cyclopentenyl group, a2-methyl-2-cyclopentenyl group, a 2-methyl-3-cyclopentenyl group, a2-methyl-4-cyclopentenyl group, a 2-methyl-5-cyclopentenyl group, a2-methylene-cyclopentyl group, a 3-methyl-1-cyclopentenyl group, a3-methyl-2-cyclopentenyl group, a 3-methyl-3-cyclopentenyl group, a3-methyl-4-cyclopentenyl group, a 3-methyl-5-cyclopentenyl group, a3-methylene-cyclopentyl group, a 1-cyclohexenyl group, a 2-cyclohexenylgroup, and a 3-cyclohexenyl group.

Examples of the alkenylene group include alkenylene groups derived fromthe above alkenyl groups.

Examples of the aryl group include C₆₋₂₀ aryl groups such as a phenylgroup, an o-methylphenyl group, an m-methylphenyl group, ap-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group,a p-chlorophenyl group, an o-fluorophenyl group, a p-mercaptophenylgroup, an o-methoxyphenyl group, a p-methoxyphenyl group, ap-aminophenyl group, a p-cyanophenyl group, an α-naphthyl group, aβ-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, ap-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthrylgroup, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthrylgroup, a 4-phenanthryl group, and a 9-phenanthryl group.

Examples of the arylene group include arylene groups derived from theabove aryl groups.

Examples of the above-exemplified groups also include organic groups inwhich the above-exemplified groups are substituted with a halogen atomsuch as a fluorine atom, a chlorine atom, a bromine atom, and an iodineatom.

By using a sulfur atom, a sulfide bond can be formed. By using an oxygenatom, an ether bond can be formed. By using an oxycarbonyl group, anester bond can be formed. By using an amido group, an amide bond can beformed. By using a secondary amino group, an amino group can be formed.By using these functional groups in combination with theabove-exemplified groups, each bond can be formed.

By using an aliphatic ring, an aliphatic cyclic structure can be formed.By using an aromatic ring, an aromatic cyclic structure can be formed.By using a Intone ring, a lactone ring structure can be formed.

Examples of the organic group having an epoxy group includeglycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, andepoxycyclohexyl.

Examples of the organic group having an acryloyl group includeacryloylmethyl, acryloylethyl, and acryloylpropyl.

Examples of the organic group having a methacryloyl group includemethacryloylmethyl, methacryloylethyl, and methacryloylpropyl.

Examples of the organic group having a mercapto group includeethylmercapto, butylmercapto, hexylmercapto, and octylmercapto.

Examples of the organic group having an amino group include aminomethyl,aminoethyl, and aminopropyl.

Examples of the organic group having a cyano group include cyanoethyland cyanopropyl.

Examples of the alkoxy group include alkoxy groups having a linear,branched, or cyclic alkyl moiety having a carbon atom number of 1 to 20,such as a methoxy group, an ethoxy group, an n-propoxy group, anisopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxygroup, a tert-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxygroup, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxygroup, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a3-methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a1-ethyl-1-methyl-n-propoxy group, and a 1-ethyl-2-methyl-n-propoxygroup, and examples of the cyclic alkoxy group include a cyclopropoxygroup, a cyclobutoxy group, a 1-methyl-cyclopropoxy group, a2-methyl-cyclopropoxy group, a cyclopentyloxy group, a1-methyl-cyclobutoxy group, a 2-methyl-cyclobutoxy group, a3-methyl-cyclobutoxy group, a 1,2-dimethyl-cyclopropoxy group, a2,3-dimethyl-cyclopropoxy group, a 1-ethyl-cyclopropoxy group, a2-ethyl-cyclopropoxy group, a cyclohexyloxy group, a1-methyl-cyclopentyloxy group, a 2-methyl-cyclopentyloxy group, a3-methyl-cyclopentyloxy group, a 1-ethyl-cyclobutoxy group, a2-ethyl-cyclobutoxy group, a 3-ethyl-cyclobutoxy group, a1,2-dimethyl-cyclobutoxy group, a 1,3-dimethyl-cyclobutoxy group, a2,2-dimethyl-cyclobutoxy group, a 2,3-dimethyl-cyclobutoxy group, a2,4-dimethyl-cyclobutoxy group, a 3,3-dimethyl-cyclobutoxy group, a1-n-propyl-cyclopropoxy group, a 2-n-propyl-cyclopropoxy group, a1-isopropyl-cyclopropoxy group, a 2-isopropyl-cyclopropoxy group, a1,2,2-trimethyl-cyclopropoxy group, a 1,2,3-trimethyl-cyclopropoxygroup, a 2,2,3-trimethyl-cyclopropoxy group, a1-ethyl-2-methyl-cyclopropoxy group, a 2-ethyl-1-methyl-cyclopropoxygroup, a 2-ethyl-2-methyl-cyclopropoxy group, and a2-ethyl-3-methyl-cyclopropoxy group.

Examples of the acyloxy group include C₂₋₂₀ acyloxy groups such as amethylcarbonyloxy group, an ethylcarbonyloxy group, ann-propylcarbonyloxy group, an isopropylcarbonyloxy group, ann-butylcarbonyloxy group, an isobutylcarbonyloxy group, asec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, ann-pentylcarbonyloxy group, a 1-methyl-n-butylcarbonyloxy group, a2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group,a 1,1-dimethyl-n-propylcarbonyloxy group, a1,2-dimethyl-n-propylcarbonyloxy group, a2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxygroup, an n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxygroup, a 2-methyl-n-pentylcarbonyloxy group, a3-methyl-n-pentylcarbonyloxy group, a 4-methyl-n-pentylcarbonyloxygroup, a 1,1-dimethyl-n-butylcarbonyloxy group, a1,2-dimethyl-n-butylcarbonyloxy group, a 1,3-dimethyl-n-butylcarbonyloxygroup, a 2,2-dimethyl-n-butylcarbonyloxy group, a2,3-dimethyl-n-butylcarbonyloxy group, a 3,3-dimethyl-n-butylcarbonyloxygroup, a 1-ethyl-n-butylcarbonyloxy group, a 2-ethyl-n-butylcarbonyloxygroup, a 1,1,2-trimethyl-n-propylcarbonyloxy group, a1,2,2-trimethyl-n-propylcarbonyloxy group, a1-ethyl-1-methyl-n-propylcarbonyloxy group, a1-ethyl-2-methyl-n-propylcarbonyloxy group, a phenylcarbonyloxy group,and a tosylcarbonyloxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, abromine atom, and an iodine atom.

Examples of the hydrolyzable silane of Formula (1) include compounds ofFormulae below.

In the above formulae, T is an alkyl group and examples of the alkylgroup include the above-exemplified alkyl groups and among them, amethyl group and an ethyl group are preferred.

In the above formulae, examples of R include the groups below.

Examples of the hydrolyzable silane of Formula (2) include compounds ofFormulae below.

In the present invention, the hydrolyzable silane contains ahydrolyzable silane of Formula (1) or a hydrolyzable silane containing acombination of a hydrolyzable silane of Formula (1) with a hydrolyzablesilane of Formula (2), and other hydrolyzable silane, and the otherhydrolyzable silane is at least one organic silicon compound selectedfrom the group consisting of Formula (3) and Formula (4).

The ratio between a hydrolyzable silane of Formula (1) or a hydrolyzablesilane containing a combination of a hydrolyzable silane of Formula (1)with a hydrolyzable silane of Formula (2), and other hydrolyzable silanemay be 1:0.1 to 100, or 1:1 to 100, or 1:1 to 50, or 1:1 to 20 in amolar ratio to be blended.

Although as the silane, a hydrolyzable silane, a hydrolysis productthereof, or a hydrolysis-condensation product thereof are contained,these compounds are preferably used as a hydrolysis-condensation product(polyorganosiloxane), and a hydrolysis-condensation product(polyorganosiloxane) of a hydrolyzable silane of Formula (1) or acombination of a hydrolyzable silane of Formula (1) with a hydrolyzablesilane of Formula (2) with a silicon-containing compound of Formula (3)is preferably used.

Examples of an alkyl group, an aryl group, a halogenated alkyl group, ahalogenated aryl group, an alkenyl group, and an organic group having anepoxy group, an acryloyl group, a methacryloyl group, a mercapto group,or a cyano group, and further an alkoxy group, an acyloxy group, and ahalogen group contained in silicon-containing compounds of Formulae (3)and (4) of R⁷, R⁸, R⁹, and R¹⁰ include those described above.

Although a hydrolyzable silane of Formula (3) does not includephenylsilane (for example, phenyltrimethoxysilane,phenyltrichlorosilane, phenyltriacetoxysilane, phenyltriethoxysilane,and phenyltriacetoxysilane) exemplified with respect to Formula (2), butincludes a substituted phenyl silane in which an aryl group of R⁷ is asubstituted phenyl group.

The aryl group as R⁷ in Formula (3) is preferably a substituted arylgroup such as a substituted phenyl group which is an alkoxyphenyl group,an acyloxyphenyl group, or an organic group containing these groups andis bonded to a silicon atom through a Si—C bond. Then, two R⁷s can forma ring with each other and can be bonded to a Si atom.

Examples of the silicon-containing compound of Formula (3) includetetramethoxysilane, tetrachlorosilane, tetraacetoxysilane,tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane,tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane,methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane,methyltriamyloxysilane, methyltriphenoxysilane,methyltribenzyloxysilane, methyltriphenethyloxysilane,glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane,α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane,β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane,α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane,β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane,γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane,α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane,γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane,δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane,(3,4-epoxycyclohexyl)methyltrimethoxysilane,(3,4-epoxycyclohexyl)methyltriethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltriethoxysilane,β-(3,4-epoxycyclohexyl)methyltripropoxysilane,β-(3,4-epoxycyclohexyl)ethyltributoxysilane,β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane,γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane,γ-(3,4-epoxycyclohexyl)propyltriethoxysilane,δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane,δ-(3,4-epoxycyclohexyl)butyltriethoxysilane,glycidoxymethylmethyldimethoxysilane,glycidoxymethylmethyldiethoxysilane,α-gycidoxyethylmethyldimethoxysilane,α-glycidoxyethylmethyldiethoxysilane,β-glycidoxyethylmethyldimethoxysilane,β-glycidoxyethylethyldimethoxysilane,α-glycidoxypropylmethyldimethoxysilane,α-glycidoxypropylmethyldiethoxysilane,β-glycidoxypropylmethyldimethoxysilane,β-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,γ-glycidoxypropylmethyldipropoxysilane,γ-glycidoxypropylmethyldibutoxysilane,γ-glycidoxypropylmethyldiphenoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,γ-glycidoxypropylvinyldimethoxysilane,γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane,ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane,vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane,methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane,methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane,methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane,methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane,methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane,methoxyphenethyltriacetoxysilane, methoxyphenethyltrichlorosilane,ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane,ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane,ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane,ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane,isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane,isopropoxyphenyltriacetoxysilane, isopropoxyphenyltrichlorosilane,isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane,isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane,tert-butoxyphenyltrimethoxysilane, tert-butoxyphenyltriethoxysilane,tert-butoxyphenyltriacetoxysilane, tert-butoxyphenyltrichlorosilane,tert-butoxybenzyltrimethoxysilane, tert-butoxybenzyltriethoxysilane,tert-butoxybenzyltriacetoxysilane, tert-butoxybenzyltrichlorosilane,methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane,methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane,ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane,ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane,γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane,γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane,γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane,chloromethyltrimethoxysilane, chloromethyltriethoxysilane,dimethyldimethoxysilane, phenylmethyldimethoxysilane,dimethyldiethoxysilane, phenylmethyldiethoxysilane,γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane,dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane,γ-methacryloxypropylmethyldiethoxysilane,γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane,methylvinyldimethoxysilane, and methylvinyldiethoxysilane.

The aryl group as R⁷ in Formula (3) is preferably a substituted arylgroup and examples thereof include a substituted phenyl group. Examplesof the substituted phenyl group include an alkoxyphenyl group, anacyloxyphenyl group, or an organic group containing any of these groups.Examples of such silanes are as follows.

Examples of the silicon-containing compound of Formula (4) includemethylenebis(trimethoxysilane), methylenebis(trichlorosilane),methylenebis(triacetoxysilane), ethylenebis(triethoxysilane),ethylenebis(trichlorosilane), ethylenebis(triacetoxysilane),propylenebis(triethoxysilane), butylenebis(trimethoxysilane),phenylenebis(trimethoxysilane), phenylenebis(triethoxysilane),phenylenebis(methyldiethoxysilane), phenylenebis(methyldimethoxysilane),naphthylenebis(trimethoxysilane), bis(trimethoxydisilane),bis(triethoxydisilane), bis(ethyldiethoxydisilane), andbis(methyldimethoxydisilane).

Specific examples of the hydrolysis-condensation product used in thepresent invention include compounds of Formulae below.

As the hydrolysis-condensation product (polyorganosiloxane) of thehydrolyzable silane, a condensation product having a weight averagemolecular weight of 1,000 to 1,000,000 or 1,000 to 100,000 can beobtained. This molecular weight is a molecular weight obtained by a GPCanalysis in terms of polystyrene.

Examples of the conditions for the GPC measurement include: using a GPCapparatus (trade name: HLC-8220GPC; manufactured by Tosoh Corporation);using a GPC column (trade names: Shodex KF803L, KF802, and KF801;manufactured by Showa Denko K.K.); using a column temperature of 40° C.;using tetrahydrofuran as the eluting liquid (eluting solvent); using aflow amount (flow rate) of 1.0 mL/min; and using polystyrene(manufactured by Showa Denko K.K.) as the standard sample.

For the hydrolysis of an alkoxysilyl group, an acyloxysilyl group, or ahalogenated silyl group, water is used in an amount of 0.5 to 100 mol,preferably 1 to 10 mol, relative to 1 mol of a hydrolyzable group.

A catalyst for the hydrolysis may be used in an amount of 0.001 to 10mol, preferably 0.001 to 1 mol, relative to 1 mol of a hydrolyzablegroup.

The reaction temperature for performing the hydrolysis and thecondensation is usually 20 to 80° C.

The hydrolysis may be performed either completely or partially. In otherwords, a hydrolysis product or a monomer may remain in thehydrolysis-condensation product thereof.

During the hydrolysis and the condensation, a catalyst may be used.

Examples of the catalyst for the hydrolysis include metal chelatecompounds, organic acids, inorganic acids, organic bases, and inorganicbases.

Examples of the metal chelate compound as the catalyst for thehydrolysis include: titanium chelate compounds such astriethoxy-mono(acetylacetonate)titanium,tri-n-propoxy-mono(acetylacetonate)titanium,triisopropoxy-mono(acetylacetonate)titanium,tri-n-butoxy-mono(acetylacetonate)titanium,tri-sec-butoxy-mono(acetylacetonate)titanium,tri-tert-butoxy-mono(acetylacetonate)titanium,diethoxy-bis(acetylacetonate)titanium,di-n-propoxy-bis(acetylacetonate)titanium,di-isopropoxy-bis(acetylacetonate)titanium,di-n-butoxy-bis(acetylacetonate)titanium,di-sec-butoxy-bis(acetylacetonate)titanium,di-tert-butoxy-bis(acetylacetonate)titanium,monoethoxy-tris(acetylacetonate)titanium,mono-n-propoxy-tris(acetylacetonate)titanium,mono-isopropoxy-tris(acetylacetonate)titanium,mono-n-butoxy-tris(acetylacetonate)titanium,mono-sec-butoxy-tris(acetylacetonate)titanium,mono-tert-butoxy-tris(acetylacetonate)titanium,tetrakis(acetylacetonate)titanium,triethoxy-mono(ethylacetoacetate)titanium,tri-n-propoxy-mono(ethylacetoacetate)titanium,tri-isopropoxy-mono(ethylacetoacetate)titanium,tri-n-butoxy-mono(ethylacetoacetate)titanium,tri-see-butoxy-mono(ethylacetoacetate)titanium,tri-tert-butoxy-mono(ethylacetoacetate)titanium,diethoxy-bis(ethylacetoacetate)titanium,di-n-propoxy-bis(ethylacetoacetate)titanium,di-isopropoxy-bis(ethylacetoacetate)titanium,di-n-butoxy-bis(ethylacetoacetate)titanium,di-sec-butoxy-bis(ethylacetoacetate)titanium,di-text-butoxy-bis(ethylacetoacetate)titanium,monoethoxy-tris(ethylacetoacetate)titanium,mono-n-propoxy-tris(ethylacetoacetate)titanium,mono-isopropoxy-tris(ethylacetoacetate)titanium,mono-n-butoxy-tris(ethylacetoacetate)titanium,mono-sec-butoxy-tris(ethylacetoacetate)titanium,mono-tert-butoxy-tris(ethylacetoacetate)titanium,tetrakis(ethylacetoacetate)titanium,mono(acetylacetonate)tris(ethylacetoacetate)titanium,bis(acetylacetonate)bis(ethylacetoacetate)titanium, andtris(acetylacetonate)mono(ethylacetoacetate)titanium; zirconium chelatecompounds such as triethoxy-mono(acetylacetonate)zirconium,tri-n-propoxy-mono(acetylacetonate)zirconium,tri-isopropoxy-mono(acetylacetonate)zirconium,tri-n-butoxy-mono(acetylacetonate)zirconium,tri-sec-butoxy-mono(acetylacetonate)zirconium,tri-tert-butoxy-mono(acetylacetonate)zirconium,diethoxy-bis(acetylacetonate)zirconium,di-n-propoxy-bis(acetylacetonate)zirconium,di-isopropoxy-bis(acetylacetonate)zirconium,di-n-butoxy-bis(acetylacetonate)zirconium,di-sec-butoxy-bis(acetylacetonate)zirconium,di-tert-butoxy-bis(acetylacetonate)zirconium,monoethoxy-tris(acetylacetonate)zirconium,mono-n-propoxy-tris(acetylacetonate)zirconium,mono-isopropoxy-tris(acetylacetonate)zirconium,mono-n-butoxy-tris(acetylacetonate)zirconium,mono-sec-butoxy-tris(acetylacetonate)zirconium,mono-tert-butoxy-tris(acetylacetonate)zirconium,tetrakis(acetylacetonate)zirconium,triethoxy-mono(ethylacetoacetate)zirconium,tri-n-propoxy-mono(ethylacetoacetate)zirconium,tri-isopropoxy-mono(ethylacetoacetate)zirconium,tri-n-butoxy-mono(ethylacetoacetate)zirconium,tri-sec-butoxy-mono(ethylacetoacetate)zirconium,tri-tert-butoxy-mono(ethylacetoacetate)zirconium,diethoxy-bis(ethylacetoacetate)zirconium,di-n-propoxy-bis(ethylacetoacetate)zirconium,di-isopropoxy-bis(ethylacetoacetate)zirconium,di-n-butoxy-bis(ethylacetoacetate)zirconium,di-sec-butoxy-bis(ethylacetoacetate)zirconium,di-tert-butoxy-bis(ethylacetoacetate)zirconium,monoethoxy-tris(ethylacetoacetate)zirconium,mono-n-propoxy-tris(ethylacetoacetate)zirconium,mono-isopropoxy-tris(ethylacetoacetate)zirconium,mono-n-butoxy-tris(ethylacetoacetate)zirconium,mono-sec-butoxy-tris(ethylacetoacetate)zirconium,mono-tert-butoxy-tris(ethylacetoacetate)zirconium,tetrakis(ethylacetoacetate)zirconium,mono(acetylacetonate)tris(ethylacetoacetate)zirconium,bis(acetylacetonate)bis(ethylacetoacetate)zirconium, andtris(acetylacetonate)mono(ethylacetoacetate)zirconium; and aluminumchelate compounds such as tris(acetylacetonate)aluminum andtris(ethylacetoacetate)aluminum.

Examples of the organic acid as the catalyst for the hydrolysis includeacetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoicacid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid,oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid,gallic acid, butyric acid, mellitic acid, arachidonic acid,2-ethylhexanoic acid, oleic acid, stearic acid, linolic acid, linoleicacid, salicylic acid, benzoic acid, p-aminobenzoic acid,p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid,dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formicacid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citricacid, and tartaric acid.

Examples of the inorganic acid as the catalyst for the hydrolysisinclude hydrochloric acid, nitric acid, sulfuric acid, hydrofluoricacid, and phosphoric acid.

Examples of the organic base as the catalyst for the hydrolysis includepyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline,trimethylamine, triethylamine, monoethanolamine, diethanolamine,dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine,diazabicyclo octane, diazabicyclo nonane, diazabicyclo undecene, andtetramethylammonium hydroxide. Examples of the inorganic base as thecatalyst for the hydrolysis include ammonia, sodium hydroxide, potassiumhydroxide, barium hydroxide, and calcium hydroxide. Among thesecatalysts, metal chelate compounds, organic acids, and inorganic acidsare preferred and these catalysts may be used singly or in combinationof two or more types thereof.

Examples of the organic solvent used for the hydrolysis include:aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane,isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane,isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbonsolvents such as benzene, toluene, xylene, ethylbenzene,trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene,diethylbenzene, isobutylbenzene, triethylbenzene, di-isopropylbenzene,n-amylnaphthalene, and trimethylbenzene; monoalcohol solvents such asmethanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol,sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol,sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol,2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanal-3,n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol,2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonylalcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol,cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzylalcohol, phenylmethylcarbinol, diacetone alcohol, and cresol;polyalcohol solvents such as ethylene glycol, propylene glycol,1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,4,hexanediol-2,5, heptanediol-2,4, 2-ethylhexanediol-1,3, diethyleneglycol, dipropylene glycol, triethylene glycol, tripropylene glycol, andglycerin; ketone solvents such as acetone, methyl ethyl ketone,methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone,methyl-isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone,methyl-n-hexyl ketone, di-isobutyl ketone, trimethylnonanone,cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone,diacetone alcohol, acetophenone, and fenchone; ether solvents such asethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexylether, ethylene oxide, 1,2-propylene oxide, dioxolane,4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethylether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether,ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether,ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutylether, ethylene glycol dibutyl ether, diethylene glycol monomethylether, diethylene glycol monoethyl ether, diethylene glycol diethylether, diethylene glycol mono-n-butyl ether, diethylene glycoldi-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycolmonomethyl ether, propylene glycol monoethyl ether, propylene glycolmonopropyl ether, propylene glycol monobutyl ether, propyleneglycolmonomethyl ether acetate, dipropylene glycol monomethyl ether,dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether,dipropylene glycol monobutyl ether, tripropylene glycol monomethylether, tetrahydrofuran, and 2-methyltetrahydrofuran; ester solvents suchas diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone,γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate,isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentylacetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutylacetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate,methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethylacetoacetate, ethyleneglycol monomethyl ether acetate, ethyleneglycolmonoethyl ether acetate, diethyleneglycol monomethyl ether acetate,diethyleneglycol monoethyl ether acetate, diethyleneglycol mono-n-butylether acetate, propyleneglycol monomethyl ether acetate, propyleneglycolmonoethyl ether acetate, propyleneglycol monopropyl ether acetate,propyleneglycol monobutyl ether acetate, dipropyleneglycol monomethylether acetate, dipropyleneglycol monoethyl ether acetate, glycoldiacetate, methoxytriglycol acetate, ethyl propionate, n-butylpropionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate,methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethylmalonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containingsolvents such as N-methylformamide, N,N-dimethylformamide,N,N-diethylformamide, acetamide, N-methylacetamide,N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone;and sulfur-containing solvents such as dimethyl sulfide, diethylsulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane,and 1,3-propane sultone. These solvents may be used singly or incombination of two or more types thereof.

Particularly preferred are ketone solvents such as acetone, methyl ethylketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone,methyl-isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone,methyl-n-hexyl ketone, di-isobutyl ketone, trimethylnonanone,cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone,diacetone alcohol, acetophenone, and fenchone in terms of the storagestability of the solution.

As an additive, bisphenol S or a bisphenol S derivative may be blendedin the composition. The blending amount of bisphenol S or a bisphenol Sderivative is 0.01 to 20 parts by mass, or 0.01 to 10 parts by mass, or0.01 to 5 parts by mass, relative to 100 parts by mass of thepolyorganosiloxane.

Preferred examples of bisphenol S or a bisphenol S derivative includethe compounds below.

The resist underlayer film forming composition of the present inventionmay contain a curing catalyst. The curing catalyst performs a functionas a curing catalyst when the coating film containing apolyorganosiloxane composed of a hydrolysis-condensation product iscured by heating.

As the curing catalyst, ammonium salts, phosphines, phosphonium salts,and sulfonium salts may be used.

Examples of the ammonium salt include: quaternary ammonium salts havinga structure of Formula (D-1):

(where m₁ is 2 to 11; n₁ is an integer of 2 to 3; R²¹ is an alkyl groupor an aryl group; and Y₁ ⁻ is an anion);

quaternary ammonium salts having a structure of Formula (D-2):

R²²R²³R²⁴R²⁵N⁺Y₁ ⁻  Formula (D-2)

(where R²², R²³, R²⁴, and R²⁵ are each an alkyl group or an aryl group;N is a nitrogen atom; Y₁ ⁻ is an anion; and R²², R²³, R²⁴, and R²⁵ areeach individually bonded to a nitrogen atom through a C—N bond);

quaternary ammonium salts having a structure of Formula (D-3):

(where R²⁶ and R²⁷ are each an alkyl group or an aryl group; and Y₁ ⁻ isan anion);

quaternary ammonium salts having a structure of Formula (D-4);

(where R²⁸ is an alkyl group or an aryl group; and is an anion);

quaternary ammonium salts having a structure of Formula (D-5):

(where R²⁹ and R³⁰ are each an alkyl group or an aryl group; and Y₁ ⁻ isan anion); and

tertiary ammonium salts having a structure of Formula (D-6):

(where m₂ is 2 to 11; n₂ is an integer of 2 to 3; H is a hydrogen atom;and Y₁ ⁻ is an anion).

Examples of the phosphonium salt include quaternary phosphonium salts ofFormula (D-7):

R¹¹R¹²R¹³R¹⁴P⁺Y₁ ⁻  Formula (D-7)

(where R¹¹, R¹², R¹³ and R¹⁴ are each an alkyl group or an aryl group; Pis a phosphorus atom; Y₁ ⁻ is an anion; and R¹¹, R¹², R¹³ and R¹⁴ areeach individually bonded to a phosphorus atom through a GP bond).

Examples of the sulfonium salt include tertiary sulfonium salts ofFormula (D-8):

R¹⁵R¹⁶R¹⁷S⁺Y₁ ⁻  Formula (D-8)

(where R¹⁵, R¹⁶, and R¹⁷ are each an alkyl group or an aryl group; S isa sulfur atom; Y₁ ⁻ is an anion; and R¹⁵, R¹⁶, and R¹⁷ are eachindividually bonded to a sulfur atom through a C—S bond).

The compound of Formula (D-1) is a quaternary ammonium salt derived froman amine. In Formula (D-1), m₁ is an integer of 2 to 11 and n₁ is aninteger of 2 to 3. R²¹ of the quaternary ammonium salt is a C₁₋₁₈,preferably C₂₋₁₀ alkyl group or a C₆₋₁₈, preferably C₆₋₁₀ aryl group andexamples thereof include: linear alkyl groups such as an ethyl group, apropyl group, and a butyl group; a benzyl group; a cyclohexyl group; acyclohexylmethyl group; and a dicyclopentadienyl group. Examples of theanion (Y₁ ⁻) include: halogen ions such as a chlorine ion (Cl⁻), abromine ion (Br⁻), and an iodine ion (I⁻); and acid groups such ascarboxylato (—COO⁻), sulfonato (—SO₃ ⁻), and alcoholate (—O⁻).

The compound of Formula (D-2) is a quaternary ammonium salt ofR²²R²³R²⁴R²⁵N⁺Y₁ ⁻, R²², R²³, R²⁴, and R²⁵ of the quaternary ammoniumsalt are each a C₁₋₁₈ alkyl group, a C₁₋₁₈ aryl group, or a silanecompound bonded to a silicon atom through an Si—C bond. Examples of theanion (Y₁ ⁻) include: halogen ions such as a chlorine ion (Cl⁻), abromine ion (Br⁻), and an iodine ion (I⁻); and acid groups such ascarboxylato (—COO⁻), sulfonato (—SO₃ ⁻) and alcoholate (—O⁻). Thequaternary ammonium salt is commercially available and examples thereofinclude tetramethylammonium acetate, tetrabutylammonium acetate,triethylbenzylammonium chloride, triethylbenzylammonium bromide,trioctylmethylammonium chloride, tributylbenzylammonium chloride, andtrimethylbenzylammonium chloride.

The compound of Formula (D-3) is a quaternary ammonium salt derived froma 1-substituted imidazole. In Formula (D-3), R²⁶ and R²⁷ are each aC₁₋₁₈ group. The sum of the numbers of carbon atoms of R²⁶ and R²⁷ ispreferably 7 or more. Examples of R²⁶ include a methyl group, an ethylgroup, a propyl group, a phenyl group, and a benzyl group and examplesof R²⁷ include a benzyl group, an octyl group, and an octadecyl group.Examples of the anion (Y₁ ⁻) include: halogen ions such as a chlorineion (Cl⁻), a bromine ion (Br⁻), and an iodine ion (I⁻); and acid groupssuch as carboxylato (—COO⁻), sulfonato (—SO₃ ⁻), and alcoholate (—O⁻).The compound is commercially available and may be produced, for example,by allowing an imidazole-based compound such as 1-methylimidazole and1-benzylimidazole to react with a halogenated alkyl or a halogenatedaryl such as benzyl bromide and methyl bromide.

The compound of Formula (D-4) is a quaternary ammonium salt derived frompyridine. In Formula (D-4), R²³ is a C₁₋₁₈, preferably C₄₋₁₈ alkyl groupor a C₁₋₁₈, preferably C₄₋₁₈ aryl group and examples thereof include abutyl group, an octyl group, a benzyl group, and a lauryl group.Examples of the anion (Y₁ ⁻) include: halogen ions such as a chlorineion (Cl⁻), a bromine ion (Br⁻), and an iodine ion (I⁻); and acid groupssuch as carboxylato (—COO⁻), sulfonato (—SO₃ ⁻), and alcoholate (—O⁻).The compound is commercially available and may be produced, for example,by allowing pyridine to react with a halogenated alkyl or a halogenatedaryl such as lauryl chloride, benzyl chloride, benzyl bromide, methylbromide, and octyl bromide. Examples of the compound includeN-laurylpyridinium chloride and N-benzylpyridinium bromide.

The compound of Formula (D-5) is a quaternary ammonium salt derived froma substituted pyridine represented by picoline and the like. In Formula(D-5), R²⁹ is a C₁₋₁₈, preferably C₄₋₁₈ alkyl group or a C₁₋₁₈,preferably C₄₋₁₈ aryl group and examples thereof include a methyl group,an octyl group, a lauryl group, and a benzyl group. R³⁰ is a C₁₋₁₈ alkylgroup or a C₁₋₁₈ aryl group and for example, when the compound is aquaternary ammonium derived from picoline, R³⁰ is a methyl group.Examples of the anion (Y₁ ⁻) include: halogen ions such as a chlorineion (Cl⁻), a bromine ion (Br⁻), and an iodine ion (I⁻); and acid groupssuch as carboxylato (—COO⁻), sulfonato (—SO₃ ⁻), and alcoholate (—O⁻).The compound is commercially available and may be produced, for example,by allowing a substituted pyridine such as picoline to react with ahalogenated alkyl or a halogenated aryl such as methyl bromide, octylbromide, lauryl chloride, benzyl chloride, and benzyl bromide. Examplesof the compound include N-benzylpicolinium chloride, N-benzylpicoliniumbromide, and N-laurylpicolinium chloride.

The compound of Formula (D-6) is a tertiary ammonium salt derived froman amine. In Formula (D-6), m₂ is an integer of 2 to 11 and n₂ is aninteger of 2 to 3. Examples of the anion (Y₁ ⁻) include: halogen ionssuch as a chlorine ion (Cl⁻), a bromine ion (Br⁻), and an iodine ion(I⁻); and acid groups such as carboxylato (—COO⁻), sulfonato (—SO₃ ⁻),and alcoholate (—O⁻). The compound may be produced by a reaction of anamine with a weak acid such as a carboxylic acid and phenol. Examples ofthe carboxylic acid include formic acid and acetic acid. When formicacid is used, the anion (Y₁ ⁻) is HCOO⁻ and when acetic acid is used,the anion (Y₁ ⁻) is CH₃COO⁻. In addition, when phenol is used, the anion(Y₁ ⁻) is C₆H₅O⁻.

The compound of Formula (D-7) is a quaternary phosphonium salt having astructure of R¹¹R¹²R¹³R¹⁴P⁺Y₁ ⁻, R¹¹, R¹², R¹³, and R¹⁴ are each a C₁₋₁₈alkyl group, a C₁₋₁₈ aryl group, or a silane compound bonded to asilicon atom through a Si—C bond. Preferably, three groups among foursubstituents of R¹¹ to R¹⁴ are a phenyl group or a substituted phenylgroup such as a phenyl group and a tolyl group and the remaining onegroup is a C₁₋₁₈ alkyl group, a C₁₋₁₈ aryl group, or a silane compoundbonded to a silicon atom through a Si—C bond. Examples of the anion (Y₁⁻) include: halogen ions such as a chlorine ion (Cl⁻), a bromine ion(Br⁻), and an iodine ion (I⁻); and acid groups such as carboxylato(—COO⁻), sulfonato (—SO₃ ⁻), and alcoholate (—O⁻). The compound iscommercially available and examples of the compound include: halogenatedtetraalkylphosphoniums such as a halogenated tetra-n-butylphosphoniumand a halogenated tetra-n-propylphosphonium; halogenatedtrialkylbenzylphosphoniums such as a halogenatedtriethylbenzylphosphonium; halogenated triphenylmonoalkylphosphoniumssuch as a halogenated triphenylmethylphosphonium and a halogenatedtriphenylethylphosphonium; halogenated triphenylbenzylphosphoniums;halogenated tetraphenylphosphoniums; halogenatedtritolylmonoarylphosphoniums; and halogenatedtritolylmonoalkylphosphoniums (the halogen atom is a chlorine atom or abromine atom). Particularly preferred examples of the compound include:halogenated triphenylmonoalkylphosphoniums such as a halogenatedtriphenylmethylphosphonium and a halogenated triphenylethylphosphonium;halogenated triphenylmonoarylphosphoniums such as a halogenatedtriphenylbenzylphosphonium; halogenated tritolylmonoarylphosphoniumssuch as a halogenated tritolylmonophenylphosphonium; and halogenatedtritolylmonoalkylphosphoniums such as a halogenatedtritolylmonomethylphosphonium (the halogen atom is a chlorine atom or abromine atom).

Examples of the phosphines include: primary phosphines such asmethylphosphine, ethylphosphine, propylphosphine, isopropylphosphine,isobutylphosphine, and phenylphosphine; secondary phosphines such asdimethylphosphine, diethylphosphine, diisopropylphosphine,diisoamylphosphine, and diphenylphosphine; and tertiary phosphines suchas trimethylphosphine, triethylphosphine, triphenylphosphine,methyldiphenylphosphine, and dimethylphenylphosphine.

The compound of Formula (D-8) is a tertiary sulfonium salt having astructure of R¹⁵R¹⁶R¹⁷S⁺Y₁ ⁻, R¹⁵, R¹⁶, and a are each a C₁₋₁₈ alkylgroup, a C₁₋₁₈ aryl group, or a silane compound bonded to a silicon atomthrough a Si—C bond. Preferably, three groups among four substituents ofR¹⁵ to R¹⁷ are a phenyl group or a substituted phenyl group such as aphenyl group and a tolyl group and the remaining one group is a C₁₋₁₈alkyl group or a C₁₋₁₈ aryl group. Examples of the anion (Y₁ ⁻) include:halogen ions such as a chlorine ion (Cl⁻), a bromine ion (Br⁻), and aniodine ion (I⁻); and acid groups such as carboxylato (—COO⁻), sulfonato(—SO₃ ⁻), and alcoholate (—O⁻). The compound is commercially availableand examples of the compound include: halogenated tetraalkylsulfoniumssuch as a halogenated tri-n-butylsulfonium and a halogenatedtri-n-propylsulfonium; halogenated trialkylbenzylsulfoniums such as ahalogenated diethylbenzylsulfonium; halogenateddiphenylmonoalkylsulfoniums such as a halogenateddiphenylmethylsulfonium and a halogenated diphenylethylsulfonium;halogenated triphenylsulfoniums, (the halogen atom is a chlorine atom ora bromine atom); tetraalkylphosphonium carboxylates such astri-n-butylsulfonium carboxylate and tri-n-propylsulfonium carboxylate;trialkylbenzylsulfonium carboxylates such as diethylbenzylsulfoniumcarboxylate; diphenylmonoalkylsulfonium carboxylates such asdiphenylmethylsulfonium carboxylate and diphenylethylsulfoniumcarboxylate; and triphenylsulfonium carboxylate. Particularly preferredare a halogenated triphenylsulfonium and triphenylsulfonium carboxylate.

The amount of the curing catalyst is 0.01 to 10 parts by mass, or 0.01to 5 parts by mass, or 0.01 to 3 parts by mass, relative to 100 parts bymass of the polyorganosiloxane.

From the hydrolysis-condensation product (polymer) obtained byhydrolyzing and condensing a hydrolyzable silane in a solvent using acatalyst, an alcohol as a by-product, the used catalyst for thehydrolysis, and the used water can be simultaneously removed bydistilling them under reduced pressure or the like. An acid catalyst ora base catalyst used for the hydrolysis can be removed by neutralizationor ion exchange. Then, with respect to the resist underlayer filmforming composition for lithography of the present invention, in theresist underlayer film forming composition containing thehydrolysis-condensation product thereof, an organic acid, water, analcohol, or a combination thereof may be blended to stabilize thecomposition.

Examples of the organic acid include oxalic acid, malonic acid,methylmalonic acid, succinic acid, maleic acid, malic acid, tartaricacid, phthalic acid, citric acid, glutaric acid, citric acid, lacticacid, and salicylic acid. Among them, oxalic acid and maleic acid arepreferred. The amount of the organic acid to be blended in thecomposition is 0.1 to 5.0 parts by mass, relative to 100 parts by massof the condensation product (polyorganosiloxane). As the water to beblended in the composition, pure water, ultrapure water, ion-exchangedwater, or the like may be used and the blending amount thereof may be 1to 20 parts by mass, relative to 100 parts by mass of the resistunderlayer film forming composition.

The alcohol to be blended in the composition is preferably an alcoholthat can be easily diffused by heating the composition after theapplication of the composition, and examples thereof include methanol,ethanol, propanol, isopropanol, and butanol. The blending amount of thealcohol may be 1 to 20 parts by mass, relative to 100 parts by mass ofthe resist underlayer film forming composition.

The resist underlayer film forming composition for lithography of thepresent invention may contain, in addition to the above mentionedcomponents, if necessary, an organic polymer compound, a photoacidgenerator, a surfactant or the like.

By using an organic polymer compound, the dry etching rate (a decreasedamount of the film thickness per unit time), the attenuationcoefficient, the refractive index, and the like of a resist underlayerfilm formed from the underlayer film forming composition for lithographyof the present invention can be controlled.

The organic polymer compound is not particularly limited and variousorganic polymers such as condensation polymerization polymers andaddition polymerization polymers may be used. As the organic polymercompound, addition polymerization polymers and condensationpolymerization polymers such as polyesters, polystyrene, polyimides,acrylic polymers, methacrylic polymers, polyvinylethers, phenolnovolacs,naphtholnovolacs, polyethers, polyamides, and polycarbonates may beused. Organic polymers having an aromatic ring structure, functioning asa light absorbing moiety, such as a benzene ring, a naphthalene ring, ananthracene ring, a triazine ring, a quinoline ring, and a quinoxalinering are preferably used.

Examples of such an organic polymer compound include additionpolymerization polymers containing as a structure unit thereof, anaddition polymerizable monomer such as benzyl acrylate, benzylmethacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate,anthrylmethyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether,and N-phenylmaleimide, and condensation polymerization polymers such asphenolnovolacs and naphtholnovolacs.

When an addition polymerization polymer is used as the organic polymercompound, the polymer compound may be either a homopolymer or acopolymer. For producing the addition polymerization polymer, anaddition polymerizable monomer is used. Examples of such an additionpolymerizable monomer include acrylic acid, methacrylic acid, acrylicacid ester compounds, methacrylic acid ester compounds, acrylamidecompounds, methacrylamide compounds, vinyl compounds, styrene compounds,maleimide compounds, maleic anhydride, and acrylonitrile.

Examples of the acrylic acid ester compound include methyl acrylate,ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexylacrylate, benzyl acrylate, phenyl acrylate, anthrylmethyl acrylate,2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate,2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate,2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutylacrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate,2-methyl-2-adamantyl acrylate,5-acryloyloxy-6-hydroxynorbornane-2-carboxylic-6-lactone,3-acryloxypropyltriethoxysilane, and glycidyl acrylate.

Examples of the methacrylic acid ester compound include methylmethacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropylmethacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenylmethacrylate, anthrylmethyl methacrylate, 2-hydroxyethyl methacrylate,2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate,2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate,4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate,tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate,5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone,3-methacryloxypropyltriethoxysilane, glycidyl methacrylate,2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenylmethacrylate.

Examples of the acrylamide compound include acrylamide,N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide,N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide.

Examples of the methacrylamide compound include methacrylamide,N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide,N-phenylmethacrylamide, N,N-dimethylmethacrylamide, andN-anthrylacrylamide.

Examples of the vinyl compound include vinyl alcohol, 2-hydroxyethylvinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether,vinylacetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether,2-methoxyethyl vinyl ether, vinylnaphthalene, and vinylanthracene.

Examples of the styrene compound include styrene, hydroxystyrene,chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, andacetylstyrene.

Examples of the maleimide compound include maleimide, N-methylmaleimide,N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, andN-hydroxyethylmaleimide.

When a condensation polymerization polymer is used as a polymer,examples of such a polymer include condensation polymerization polymersof a glycol compound and a dicarboxylic acid compound. Examples of theglycol compound include diethylene glycol, hexamethylene glycol, andbutylene glycol. Examples of the dicarboxylic acid compound includesuccinic acid, adipic acid, terephthalic acid, and maleic anhydride.Examples of the polymer also include polyesters, polyamides, andpolyimides such as polypyromellitimide,poly(p-phenyleneterephthalamide), polybutylene terephthalate, andpolyethylene terephthalate.

When the organic polymer compound contains a hydroxy group, the hydroxygroup can cause a crosslinking reaction with a polyorganosiloxane.

As the organic polymer compound, a polymer compound having a weightaverage molecular weight of, for example, 1,000 to 1,000,000, or 3,000to 300,000, or 5,000 to 200,000, or 10,000 to 100,000 may be used.

The organic polymer compounds may be used singly or in combination oftwo or more types thereof.

When the organic polymer compound is used, the content thereof is 1 to200 parts by mass, or 5 to 100 parts by mass, or 10 to 50 parts by mass,or 20 to 30 parts by mass, relative to 100 parts by mass of thecondensation product (polyorganosiloxane).

The resist underlayer film forming composition of the present inventionmay contain an acid generator.

Examples of the acid generator include thermoacid generators andphotoacid generators.

The photoacid generator generates an acid during exposure of the resist.Therefore, the acidity of the underlayer film can be controlled. This isone method for adjusting the acidity of the underlayer film to that ofthe resist as an upper layer of the underlayer film. By adjusting theacidity of the underlayer film, the pattern shape of the resist formedin the upper layer can be controlled.

Examples of the photoacid generator contained in the resist underlayerfilm forming composition of the present invention include onium saltcompounds, sulfonimide compounds, and disulfonyl diazomethane compounds.

Examples of the onium salt compound include: iodonium salt compoundssuch as diphenyliodoniumhexafluorophosphate,diphenyliodoniumtrifluoromethanesulfonate, diphenyliodoniumnonafluoron-butane sulfonate, diphenyliodoniumperfluoro n-octane sulfonate,diphenyliodoniumcamphorsulfonate,bis(4-tert-butylphenyl)iodoniumcamphorsulfonate, andbis(4-tert-butylphenyl)iodoniumtrifluoromethanesulfonate; and sulfoniumsalt compounds such as triphenylsulfoniumhexafluoroantimonate,triphenylsulfoniumnonafluoro n-butane sultanate,triphenylsulfoniumcamphorsulfonate, andtriphenylsulfoniumtrifluoromethanesulfonate.

Examples of the sulfonimide compound includeN-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, andN-(trifluoromethanesulfonyloxy)naphthalimide.

Examples of the disulfonyldiazomethane compound includebis(trifluoromethylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane,bis(p-toluenesufonyl)diazomethane,bis(2,4-dimethylbenzenesulfonyl)diazomethane, andmethylsulfonyl-p-toluenesulfonyldiazomethane.

These photoacid generators may be used singly or in combination of twoor more types thereof.

When the photoacid generator is used, the content thereof is 0.01 to 5parts by mass, or 0.1 to 3 parts by mass, or 0.5 to 1 part by mass,relative to 100 parts by mass of the condensation product(polyorganosiloxane).

The surfactant is effective in suppressing the formation of a pin hole,a striation, and the like when the resist underlayer film formingcomposition for lithography of the present invention is applied onto asubstrate.

Examples of the surfactant contained in the resist underlayer filmforming composition of the present invention include: nonionicsurfactants, for example, polyoxyethylene alkyl ethers such aspolyoxyethylene lauryl ether, polyoxyethylene stearyl ether,polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether,polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenolether and polyoxyethylene nonylphenol ether,polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acidesters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitanmonostearate, sorbitan monooleate, sorbitan trioleate, and sorbitantristearate, polyoxyethylene sorbitan fatty acid esters such aspolyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitanmonopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylenesorbitan trioleate, and polyoxyethylene sorbitan tristearate;fluorinated surfactants, for example, EFTOP EF301, EF303, and EF352(trade names; manufactured by Tohkem Products Corp.), MEGAFAC F171,F173, R-08, and R-30 (trade names; manufactured by Dainippon Ink &Chemicals Inc.), Fluorad FC430 and FC431 (trade names; manufactured bySumitomo 3M Limited), AsahiGuard AG710 and Surflon S-382, SC101, SC102,SC103, SC104, SC105, and SC106 (trade names; manufactured by Asahi GlassCo., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-EtsuChemical Co., Ltd.). These surfactants may be used singly or incombination of two or more types thereof. When the surfactant is used,the content thereof is 0.0001 to 5 parts by mass, or 0.001 to 1 part bymass, or 0.01 to 0.5 part by mass, relative to 100 parts by mass of thecondensation product (polyorganosiloxane).

In the resist underlayer film forming composition of the presentinvention, a rheology controlling agent and an adhesion assistant may beblended. The rheology controlling agent is effective in enhancing thefluidity of the underlayer film forming composition. The adhesionassistant is effective in enhancing the adhesion of the underlayer filmto the semiconductor substrate or the resist.

The solvent used for the resist underlayer film forming composition ofthe present invention is not particularly limited to be used so long asthe solvent can dissolve the solid content. Examples of such a solventinclude methyl cellosolve acetate, ethyl cellosolve acetate, propyleneglycol, propylene glycol monomethyl ether, propylene glycol monoethylether, methylisobutylcarbinol, propylene glycol monobutyl ether,propylene glycol monomethyl ether acetate, propylene glycol monoethylether acetate, propylene glycol monopropyl ether acetate, propyleneglycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone,cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate,methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl3-methoxypropionate, ethyl 3-ethoxypropionate, methyl3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycolmonomethyl ether, ethylene glycol monoethyl ether, ethylene glycolmonopropyl ether, ethylene glycol monobutyl ether, ethylene glycolmonomethyl ether acetate, ethylene glycol monoethyl ether acetate,ethylene glycol monopropyl ether acetate, ethylene glycol monobutylether acetate, diethylene glycol dimethyl ether, diethylene glycoldiethyl ether, diethylene glycol dipropyl ether, diethylene glycoldibutyl ether, propylene glycol monomethyl ether, propylene glycoldimethyl ether, propylene glycol diethyl ether, propylene glycoldipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyllactate, isopropyl lactate, butyl lactate, isobutyl lactate, methylformate, ethyl formate, propyl formate, isopropyl formate, butylformate, isobutyl formate, amyl formate, isoamyl formate, methylacetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate,methyl propionate, ethyl propionate, propyl propionate, isopropylpropionate, butyl propionate, isobutyl propionate, methyl butyrate,ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate,isobutyl butyrate, ethyl hydroxyacetate, ethyl2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate,methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethylethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate,ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropylacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate,toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butylketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone,N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide,N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. Thesesolvents may be used singly or in combination of two or more typesthereof.

Hereinafter, the use of the resist underlayer film forming compositionof the present invention is described.

By using the resist underlayer film forming composition of the presentinvention, the resist underlayer film is formed by an coating methodeither on a substrate or on an organic underlayer film on a substrate,and on the resist underlayer film, a resist film (for example, aphotoresist or an electron beam resist) is formed. Then, a resistpattern is formed by exposure and development. By dry etching the resistunderlayer film using the resist pattern to transfer the pattern, thesubstrate is processed by the transferred pattern. Alternatively, byetching the organic underlayer film to transfer the pattern, thesubstrate is processed by the etched organic underlayer film.

In forming a fine pattern, for preventing a pattern collapse, the resistfilm thickness tends to become smaller. Due to the thinning of theresist, the dry etching for transferring the pattern to a film existingas an underlayer of the resist cannot transfer the pattern unless theetching rate of the underlayer film is higher than that of the upperlayer film. An organic component film and an inorganic component filmhave significantly different dry etching rates from each other dependingon the selection of the etching gas. The dry etching rate of the organiccomponent film is enhanced by an oxygen-based gas and the dry etchingrate of the inorganic component film is enhanced by using ahalogen-containing gas.

Accordingly, for example, a resist pattern is formed and transferred tothe resist underlayer film formed from the resist underlayer filmforming composition of the present invention existing as the underlayerof the resist pattern by dry etching the resist underlayer film with ahalogen-containing gas, and the substrate is processed with ahalogen-containing gas using the pattern transferred to the resistunderlayer film. Alternatively, by dry etching the organic underlayerfilm existing as the underlayer of the resist underlayer film to whichthe pattern has been transferred with an oxygen-based gas using theresist underlayer film, the pattern is transferred to the organicunderlayer film, and the substrate is processed with ahalogen-containing gas using the organic underlayer film to which thepattern has been transferred.

The resist underlayer film forming composition of the present inventionis applied onto a substrate used in the production of semiconductordevices (for example, silicon wafer substrates, substrates coated withsilicon/silicon dioxide, silicon nitride substrates, glass substrates,ITO substrates, polyimide substrates, substrates coated with a lowdielectric constant material (low-k material)) by an appropriate coatingmethod such as a spinner and a coater and then, is baked to form aresist underlayer film. The baking conditions are appropriately selectedfrom baking temperatures of 80° C. to 250° C. and baking time of 0.3 to60 minutes. Preferably, the baking temperature is 150° C. to 250° C. andthe baking time is 0.5 to 2 minutes. Here, the formed underlayer filmhas a film thickness of, for example, 10 to 1,000 nm, or 20 to 500 nm,or 50 to 300 nm, or 100 to 200 nm.

Next, on the resist underlayer film, for example, a photoresist layer isformed. The formation of the photoresist layer may be performed by aknown method, that is, by applying a photoresist composition solutiononto the underlayer film and by baking the composition solution. Thephotoresist has a film thickness of, for example, 50 to 10,000 nm, or100 to 2,000 nm, or 200 to 1,000 nm.

In the present invention, after the organic underlayer film is formed onthe substrate, the resist underlayer film may be formed from thecomposition of the present invention on the organic underlayer film andfurther, the resist underlayer film may be coated with the photoresist.Thus, even when the pattern width of the photoresist becomes smaller andthe resist underlayer film is coated thinly with the photoresist forpreventing a pattern collapse, the processing of the substrate may beperformed by selecting an appropriate etching gas. For example, theresist underlayer film of the present invention may be processed with afluorine-based gas as an etching gas having a sufficiently higheretching rate of the resist underlayer film than that of the photoresist,and the organic underlayer film may be processed with an oxygen-basedgas as an etching gas having a sufficiently higher etching rate of theorganic underlayer film than that of the resist underlayer film of thepresent invention. Furthermore, the substrate may be processed with afluorine-based gas as an etching gas having a sufficiently higheretching rate of the substrate than that of the organic underlayer film.

The photoresist formed on the resist underlayer film of the presentinvention is not particularly limited so long as the photoresist issensitive to light used for exposure, and both a negative-typephotoresist and a positive-type photoresist may be used. Examples of thephotoresist include: a positive-type photoresist made of a novolac resinand 1,2-naphthoquinonediazide sulfonic acid ester; a chemicalamplification-type photoresist made of a binder having a group elevatingthe alkali dissolving rate by being decomposed by an acid, and aphotoacid generator; a chemical amplification-type photoresist made of alow molecular compound elevating the alkali dissolving rate of thephotoresist by being decomposed by an acid, an alkali-soluble binder,and a photoacid generator; and a chemical amplification-type photoresistmade of a binder having a group elevating the alkali dissolving rate bybeing decomposed by an acid, a low molecular compound elevating thealkali dissolving rate of the photoresist by being decomposed by anacid, and a photoacid generator. Examples of the photoresist includetrade name: APEX-E manufactured by Shipley Company, L.L.C., trade name:PAR710 manufactured by Sumitomo Chemical Co., Ltd., and trade name:SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. The examples alsoinclude fluorine atom-containing polymer-based photoresists described inProc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364(2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

Next, the exposure is performed through a predetermined mask. For theexposure, a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser(wavelength: 193 nm), a F2 excimer laser (wavelength: 157 nm), or thelike may be used. After exposure, if necessary, post exposure bake mayalso be performed. The post exposure bake is performed under conditionsappropriately selected from baking temperatures of 70° C. to 150° C. andbaking time of 0.3 to 10 minutes.

In the present invention, as the resist, a resist for electron beamlithography or a resist for EUV lithography may be used instead of thephotoresist. As the electron beam resist, both a positive type and anegative type may be used. Examples of the electron beam resist include:a chemical amplification-type resist made of an acid generator and abinder having a group changing the alkali dissolving rate by beingdecomposed by an acid; a chemical amplification-type resist made of analkali-soluble binder, an acid generator, and a low molecular compoundchanging the alkali dissolving rate of the resist by being decomposed byan acid; a chemical amplification-type resist made of an acid generator,a binder having a group changing the alkali dissolving rate by beingdecomposed by an acid, and a low molecular compound changing the alkalidissolving rate of the resist by being decomposed by an acid; anon-chemical amplification-type resist made of a binder having a groupchanging the alkali dissolving rate by being decomposed by an electronbeam; and a non-chemical amplification-type resist made of a binderhaving a moiety changing the alkali dissolving rate by being broken byan electron beam. Also in the case of using the electron beam resist, aresist pattern can be formed in a manner similar to that in the case ofusing a photoresist, by using an electron beam as the irradiationsource.

As the EUV resist, a methacrylate resin-based resist may be used.

Next, the development is performed by using a developer (for example, analkaline developer). Consequently, for example when a positive-typephotoresist is used, the photoresist of an exposed part is removed toform a photoresist pattern.

Examples of the developer include alkaline aqueous solutions such as:aqueous solutions of alkali metal hydroxides such as potassium hydroxideand sodium hydroxide; aqueous solutions of quaternary ammoniumhydroxides such as tetramethylammonium hydroxide, tetraethylammoniumhydroxide, and choline; and aqueous solutions of amines such asethanolamine, propylamine, and ethylenediamine. Furthermore, in thesedevelopers, a surfactant or the like may also be blended. The conditionsfor development are appropriately selected from temperatures of 5 to 50°C. and time of 10 to 600 seconds.

In the present invention, as the developer, an organic solvent may beused. After exposure, development is performed by using a developer(solvent). By development, for example, when a positive-type photoresistis used, the photoresist of an unexposed part is removed to form aphotoresist pattern.

Examples of the developer include methyl acetate, butyl acetate, ethylacetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethylmethoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl etheracetate, ethylene glycol monoethyl ether acetate, ethylene glycolmonopropyl ether acetate, ethylene glycol monobutyl ether acetate,ethylene glycol monophenyl ether acetate, diethylene glycol monomethylether acetate, diethylene glycol monopropyl ether acetate, diethyleneglycol monoethyl ether acetate, diethylene glycol monophenyl etheracetate, diethylene glycol monobutyl ether acetate, diethylene glycolmonoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate,4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate,3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl etheracetate, propylene glycol monoethyl ether acetate, propylene glycolmonopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate,4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentylacetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate,3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate,4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methylformate, ethyl formate, butyl formate, propyl formate, ethyl lactate,butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butylcarbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butylpyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate,ethyl propionate, propyl propionate, isopropyl propionate, methyl2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl3-methoxypropionate, ethyl 3-methoxypropionate, ethyl3-ethoxypropionate, and propyl 3-methoxypropionate. Furthermore, inthese developers, a surfactant or the like may also be blended. Theconditions for development are appropriately selected from temperaturesof 5 to 50° C. and time of 10 to 600 seconds.

Then, using the pattern of the photoresist (upper layer) thus formed asa protecting film, the removal of the resist underlayer film(intermediate layer) of the present invention is performed and next,using the film composed of the patterned photoresist and the patternedresist underlayer film (intermediate layer) of the present invention asa protecting film, the removal of the organic underlayer film(underlayer) is performed. Finally, using the patterned resistunderlayer film (intermediate layer) of the present invention and thepatterned organic underlayer film (underlayer) as a protecting film, theprocessing of the semiconductor substrate is performed.

First, the resist underlayer film (intermediate layer) of the presentinvention at the part where the photoresist is removed is removed by dryetching to expose the semiconductor substrate. For dry etching of theresist underlayer film of the present invention, gases such astetrafluoromethane (CF₄), perfluorocyclobutane (C₄F₈), perfluoropropane(C₃F₈), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen,sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorinetrifluoride, chlorine, trichloroborane and dichloroborane may be used.For dry etching the resist underlayer film, a halogen-based gas ispreferably used. By dry etching with a halogen-based gas, fundamentally,a photoresist that is composed of organic substances is difficult to beremoved. On the contrary, the resist underlayer film of the presentinvention containing a large amount of silicon atoms is promptly removedby using a halogen-based gas. Therefore, the decrease in the filmthickness of the photoresist due to dry etching of the resist underlayerfilm can be suppressed. As the result thereof, the photoresist may beused as a thin film. The resist underlayer film is dry-etched preferablywith a fluorine-based gas and examples of the fluorine-based gas includetetrafluoromethane (CF₄), perfluorocyclobutane (C₄F₈), perfluoropropane(C₃F₈), trifluoromethane, and difluoromethane (CH₂F₂).

Subsequently, using the film composed of the patterned photoresist andthe patterned resist underlayer film of the present invention as aprotecting film, the removal of the organic underlayer film isperformed. The removal of the organic underlayer film (underlayer) isperformed by dry etching preferably with an oxygen-based gas. This isbecause the resist underlayer film of the present invention containing alarge amount of silicon atoms is difficult to be removed by dry etchingwith an oxygen-based gas.

Finally, the processing of the semiconductor substrate is performed. Theprocessing of the semiconductor substrate is performed by dry etchingpreferably with a fluorine-based gas.

Examples of the fluorine-based gas include tetrafluoromethane (CF₄),perfluorocyclobutane (C₄F₈), perfluoropropane (C₃F₈), trifluoromethane,and difluoromethane (CH₂F₂).

As an upper layer of the resist underlayer film of the presentinvention, an organic anti-reflective coating can be formed before theformation of the photoresist. The anti-reflective coating compositionused here is not particularly limited and may be optionally selected tobe used from the compositions commonly used in a conventionallithography process. The formation of the anti-reflective coating may beperformed by a commonly used method, for example, by applying ananti-reflective coating composition by a spinner or a coater and bybaking the composition.

The substrate onto which the resist underlayer film forming compositionof the present invention is applied may also be a substrate having anorganic or inorganic anti-reflective coating formed by a CVD method onits surface and, on the anti-reflective coating, the underlayer film ofthe present invention can also be formed.

A resist underlayer film formed from the resist underlayer film formingcomposition of the present invention may absorb light used in alithography process depending on the wavelength of light. Then, in sucha case, the resist underlayer film can function as an anti-reflectivecoating having the effect of preventing light reflected on thesubstrate. Furthermore, the underlayer film of the present invention mayalso be used as a layer for preventing an interaction between thesubstrate and the photoresist, a layer having a function of preventingan adverse action of a material used in the photoresist or an adverseaction of a substance generated during exposure of the photoresistagainst the substrate, a layer having a function of preventing thediffusion of a substance generated in or on the substrate during heatingand baking to the upper layer photoresist, a barrier layer for reducinga poisoning effect to the photoresist layer by a semiconductor substratedielectric layer, and the like.

A resist underlayer film formed from the resist underlayer film formingcomposition may be applied to a substrate in which a via hole used inthe dual damascene process is formed to be used as an embedding materialcapable of filling the hole without any void. The resist underlayer filmmay also be used as a planarizing material for planarizing the surfaceof a semiconductor substrate having unevenness.

The above resist underlayer film may be used as an underlayer film of anEUV resist also for the following purpose besides the purpose of thefunction as a hardmask. The above resist underlayer film formingcomposition may be used as an EUV resist underlayer anti-reflectivecoating capable of preventing a reflection of exposure light undesirableduring EUV exposure (wavelength: 13.5 nm) such as UV and DUV (ArF lightand KrF light) on the substrate or the interface without causingintermixing with the EUV resist. The above resist underlayer filmforming composition can efficiently prevent light reflection as anunderlayer of an EUV resist. When the above resist underlayer filmforming composition is used as the EUV resist underlayer film, theprocess can be performed in a manner similar to that in the case of anunderlayer film for a photoresist.

EXAMPLES Synthesis of Compound 1

Into a 200 mL four-neck flask equipped with a magnetic stirrer, 15.00 gof methyl 5-norbornene-2-carboxylate, 3.76 g of Karstedt's catalyst (a2% by mass xylene solution of aplatinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex), and 112g of toluene were charged and into the resultant reaction mixture, 17.81g of triethoxysilane was added dropwise over 10 minutes. At roomtemperature, the resultant reaction mixture was stirred for 5 hours andthe resultant reaction liquid was concentrated and dried, followed bypurifying the resultant crude product by distillation under reducedpressure to obtain a compound 1.

¹H-NMR (500 MHz) in DMSO-d₆: 0.62-0.79 ppm (m, 111), 1.12-1.79 ppm (m,15H), 2.20-2.50 ppm (m, 3H), 3.57 ppm (q, 3H), 3.70-3.77 ppm (m, 6H)

Synthesis of Compound 2

Into a 200 mL four-neck flask equipped with a magnetic stirrer, 15.00 gof methyl 3,3-dimethyl-4-pentenoate, 1.91 g of Karstedt's catalyst (a 2%by mass xylene solution of aplatinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex), and 112g of toluene were charged and into the resultant mixture, 19.06 g oftriethoxysilane was added dropwise over 10 minutes. At room temperature,the resultant reaction mixture was stirred for 5 hours and the resultantreaction liquid was concentrated and dried, followed by purifying theresultant crude product by distillation under reduced pressure to obtaina compound 2.

¹H-NMR (500 MHz) in DMSO-d₆: 0.50 ppm (t, 2H), 0.90 ppm (s, 6H), 1.15ppm (q, 914), 1.31 ppm (quint, 2H), 2.22 ppm (s, 2H), 3.56 ppm (s, 3H),3.73 ppm (q, 6H)

Synthesis of Compound 3

Into a 200 mL four-neck flask equipped with a magnetic stirrer, 15.00 gof diethyl allylmalonate, 1.91 g of Karstedt's catalyst (a 2% by massxylene solution of aplatinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex), and 112g of toluene were charged and into the resultant reaction mixture, 13.54g of triethoxysilane was added dropwise over 10 minutes. At roomtemperature, the resultant reaction mixture was stirred for 5 hours andthe resultant reaction liquid was concentrated and dried, followed bypurifying the resultant crude product by distillation under reducedpressure to obtain a compound 3.

¹H-NMR (500 MHz) in DMSO-d₆: 0.66 ppm (t, 2H), 1.15 ppm (q, 9H), 1.32ppm (quint, 2H), 1.78 ppm (q, 2H), 3.47 ppm (t, 1H), 3.73 ppm (t, 6H),4.11 ppm (t, 4H)

Synthesis of Compound 4

Into a 200 mL four-neck flask equipped with a magnetic stirrer, 8.01 gof sodium tert-butoxide and 100 g of THF (tetrahydrofuran) were chargedand while maintaining the temperature inside the reaction vessel at 17°C. or lower, into the resultant reaction mixture, 18.03 g of diisopropylmalonate was added dropwise. After the completion of the addition, intothe reaction vessel, 10.09 g of allyl bromide was added and the reactionmixture was stirred as it was. The reaction solution was subjected toextraction with water and tert-butyl methyl ether, and the extract waspurified by distillation under reduced pressure to obtain diisopropylallylmalonate as a reaction intermediate.

¹H-NMR (500 MHz) in CDCl₃: 1.20-1.27 ppm (m, 12H), 2.62 ppm (t, 2H),3.34 ppm (m, 1H), 5.02-5.14 ppm (m, 4H), 5.77-5.92 ppm (m, 1H)

Into a 200 mL four-neck flask equipped with a magnetic stirrer, 10.00 gof diisopropyl allylmalonate, 1.91 g of Karstedt's catalyst (a 2% bymass xylene solution of aplatinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex), and75.00 g of toluene were charged and into the resultant reaction mixture,7.92 g of triethoxysilane was added dropwise over 10 minutes. At roomtemperature, the resultant reaction mixture was stirred for 5 hours andthe resultant reaction liquid was concentrated and dried, followed bypurifying the resultant crude product by distillation under reducedpressure to obtain a compound 4.

¹H-NMR (500 MHz) in DMSO-d₆: 0.56 ppm (t, 2H), 1.11-1.18 ppm (m, 21H),1.18 ppm (quint, 2H), 1.76 ppm (q, 2H), 3.34-3.39 ppm (m, 1H), 3.72 ppm(q, 6H), 4.90-4.95 ppm (m, 2H)

Synthesis of Compound 5

Into a 200 mL four-neck flask equipped with a magnetic stirrer, 8.01 gof sodium tert-butoxide and 100 g of THF (tetrahydrofuran) were chargedand while maintaining the temperature inside the reaction vessel at 17°C. or lower, into the resultant reaction mixture, 18.03 g ofdi-tert-propyl malonate was added dropwise. After the completion of theaddition, into the reaction vessel, 10.09 g of allyl bromide was addedand the reaction mixture was stirred as it was. The reaction solutionwas subjected to extraction with water and tert-butyl methyl ether, andthe extract was purified by distillation under reduced pressure toobtain di-tert-butyl allylmalonate as a reaction intermediate.

¹H-NMR (500 MHz) in CDCl₃: 1.48 ppm (s, 18H), 2.55 ppm (t, 2H),3.18-3.24 ppm (m, 1H), 5.02-5.14 ppm (m, 2H), 5.79-5.92 ppm (m, 1H)

Into a 200 mL four-neck flask equipped with a magnetic stirrer, 10.00 gof di-tert-butyl allylmalonate, 1.91 g of Karstedt's catalyst (a 2% bymass xylene solution of aplatinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex), and75.00 g of toluene were charged and into the resultant reaction mixture,7.05 g of triethoxysilane was added dropwise over 10 minutes. At roomtemperature, the resultant reaction mixture was stirred for 5 hours andthe resultant reaction liquid was concentrated and dried, followed bypurifying the resultant crude product by distillation under reducedpressure to obtain a compound 5.

¹H-NMR (500 MHz) in DMSO-d₆: 0.56 ppm (t, 2H), 1.13 ppm (t, 9H),1.31-1.41 ppm (m, 20H), 1.69 ppm (q, 2H), 2.16-3.22 ppm (m, 1H), 3.73ppm (q, 6H)

Synthesis Example 1

15.40 g (75 mol % in all silanes) of tetraethoxysilane, 1.23 g (7 mol %in all silanes) of methyltriethoxysilane, 1.37 g (7 mol % in allsilanes) of phenyltrimethoxysilane, 1.72 g (6 mol % in all silanes) ofmethylsulfonyl methylphenyl trimethoxysilane, 1.62 g (5 mol % in allsilanes) of (5-(triethoxysilyl)norbornene-2,3-dicarboxylic anhydride,and 32.00 g of acetone were charged into a 100 mL flask. While theresultant mixture solution was stirred with a magnetic stirrer, 6.66 gof a 0.01 mol/L hydrochloric acid was added dropwise into the mixturesolution. After the completion of the addition, the flask wastransferred into an oil bath adjusted to 85° C., and underwarming-reflux, the reaction was effected for 240 minutes. Then, thereaction solution was cooled down to room temperature and to thereaction solution, 21 g of propylene glycol monomethyl ether acetate wasadded. From the resultant reaction solution, ethanol as a reactionby-product, water, and hydrochloric acid were distilled off underreduced pressure and the resultant reaction mixture was concentrated toobtain a hydrolysis-condensation product (polymer) propylene glycolmonomethyl ether acetate solution. To the obtained solution, propyleneglycol monoethyl ether was added to adjust the resultant solution tocontain a solid residue in a proportion of 15% by weight at 140° C.while the solvent ratio of propylene glycol monomethyl etheracetatepropylene glycol monoethyl ether was 20/80. The obtained polymercorresponded to Formula (5-1) and had a weight average molecular weightmeasured by GPC of Mw 1,600 in terms of polystyrene.

Synthesis Example 2

15.48 g (75 mol % in all silanes) of tetraethoxysilane, 1.24 g (7 mol %in all silanes) of methyltriethoxysilane, 1.37 g (7 mol % in allsilanes) of phenyltrimethoxysilane, 1.73 g (6 mol % in all silanes) ofmethylsulfonyl methylphenyl trimethoxysilane, 1.51 g (5 mol % in allsilanes) of 3-(triethoxysilyl)propylsuccinic anhydride, and 31.98 g ofacetone were charged into a 100 mL flask. While the resultant mixturesolution was stirred with a magnetic stirrer, 6.69 g of a 0.01 mol/Lhydrochloric acid was added dropwise into the mixture solution. Afterthe completion of the addition, the flask was transferred into an oilbath adjusted to 85° C., and under warming-reflux, the reaction waseffected for 240 minutes. Then, the reaction solution was cooled down toroom temperature and to the reaction solution, 21 g of propylene glycolmonomethyl ether acetate was added. From the resultant reactionsolution, ethanol as a reaction by-product, water, and hydrochloric acidwere distilled off under reduced pressure and the resultant reactionmixture was concentrated to obtain a hydrolysis-condensation product(polymer) propylene glycol monomethyl ether acetate solution. To theobtained solution, propylene glycol monoethyl ether was added to adjustthe resultant solution to contain a solid residue in a proportion of 15%by weight at 140° C. while the solvent ratio of propylene glycolmonomethyl ether acetatepropylene glycol monoethyl ether was 20/80. Theobtained polymer corresponded to Formula (5-2) and had a weight averagemolecular weight measured by GPC of Mw 1,600 in terms of polystyrene.

Synthesis Example 3

15.44 g (75 mol % in all silanes) of tetraethoxysilane, 1.23 g (7 mol %in all silanes) of methyltriethoxysilane, 1.37 g (7 mol % in allsilanes) of phenyltrimethoxysilane, 1.72 g (6 mol % in all silanes) ofmethylsulfonyl methylphenyl trimethoxysilane, 1.56 g (5 mol % in allsilanes) of the compound 1, and 31.99 g of acetone were charged into a100 mL flask. While the resultant mixture solution was stirred with amagnetic stirrer, 6.68 g of a 0.01 mol/L hydrochloric acid was addeddropwise into the mixture solution. After the completion of theaddition, the flask was transferred into an oil bath adjusted to 85° C.,and under warming-reflux, the reaction was effected for 240 minutes.

Then, the reaction solution was cooled down to room temperature and tothe reaction solution, 21 g of propylene glycol monomethyl ether acetatewas added. From the resultant reaction solution, ethanol as a reactionby-product, water, and hydrochloric acid were distilled off underreduced pressure and the resultant reaction mixture was concentrated toobtain a hydrolysis-condensation product (polymer) propylene glycolmonomethyl ether acetate solution. To the obtained solution, propyleneglycol monoethyl ether was added to adjust the resultant solution tocontain a solid residue in a proportion of 15% by weight at 140° C.while the solvent ratio of propylene glycol monomethyl etheracetatepropylene glycol monoethyl ether was 20/80. The obtained polymercorresponded to Formula (5-3) and had a weight average molecular weightmeasured by GPC of Mw 1,600 in terms of polystyrene.

Synthesis Example 4

15.47 g (75 mol % in all silanes) of tetraethoxysilane, 1.24 g (7 mol %in all silanes) of methyltriethoxysilane, 1.37 g (7 mol % in allsilanes) of phenyltrimethoxysilane, 1.73 g (6 mol % in all silanes) ofmethylsulfonyl methylphenyl trimethoxysilane, 1.52 g (5 mol % in allsilanes) of the compound 2, and 31.99 g of acetone were charged into a100 mL flask. While the resultant mixture solution was stirred with amagnetic stirrer, 6.69 g of a 0.01 mol/L hydrochloric acid was addeddropwise into the mixture solution. After the completion of theaddition, the flask was transferred into an oil bath adjusted to 85° C.,and under warming-reflux, the reaction was effected for 240 minutes.

Then, the reaction solution was cooled down to room temperature and tothe reaction solution, 21 g of propylene glycol monomethyl ether acetatewas added. From the resultant reaction solution, ethanol as a reactionby-product, water, and hydrochloric acid were distilled off underreduced pressure and the resultant reaction mixture was concentrated toobtain a hydrolysis-condensation product (polymer) propylene glycolmonomethyl ether acetate solution. To the obtained solution, propyleneglycol monoethyl ether was added to adjust the resultant solution tocontain a solid residue in a proportion of 15% by weight at 140° C.while the solvent ratio of propylene glycol monomethyl etheracetatepropylene glycol monoethyl ether was 20/80. The obtained polymercorresponded to Formula (5-4) and had a weight average molecular weightmeasured by GPC of Mw 1,600 in terms of polystyrene.

Synthesis Example 5

15.29 g (75 mol % in all silanes) of tetraethoxysilane, 1.22 g (7 mol %in all silanes) of methyltriethoxysilane, 1.36 g (7 mol % in allsilanes) of phenyltrimethoxysilane, 1.70 g (6 mol % in all silanes) ofmethylsulfonyl methylphenyl trimethoxysilane, 1.78 g (5 mol % in allsilanes) of the compound 3, and 32.03 g of acetone were charged into a100 mL flask. While the resultant mixture solution was stirred with amagnetic stirrer, 6.61 g of a 0.01 mol/L hydrochloric acid was addeddropwise into the mixture solution. After the completion of theaddition, the flask was transferred into an oil bath adjusted to 85° C.,and under warming-reflux, the reaction was effected for 240 minutes.Then, the reaction solution was cooled down to room temperature and tothe reaction solution, 21 g of propylene glycol monomethyl ether acetatewas added. From the resultant reaction solution, ethanol as a reactionby-product, water, and hydrochloric acid were distilled off underreduced pressure and the resultant reaction mixture was concentrated toobtain a hydrolysis-condensation product (polymer) propylene glycolmonomethyl ether acetate solution. To the obtained solution, propyleneglycol monoethyl ether was added to adjust the resultant solution tocontain a solid residue in a proportion of 15% by weight at 140° C.while the solvent ratio of propylene glycol monomethyl etheracetatepropylene glycol monoethyl ether was 20/80. The obtained polymercorresponded to Formula (5-5) and had a weight average molecular weightmeasured by GPC of Mw 1,600 in terms of polystyrene.

Synthesis Example 6

15.20 g (75 mol % in all silanes) of tetraethoxysilane, 1.21 g (7 mol %in all silanes) of methyltriethoxysilane, 1.35 g (7 mol % in allsilanes) of phenyltrimethoxysilane, 1.70 g (6 mol % in all silanes) ofmethylsulfonyl methylphenyl trimethoxysilane, 1.70 g (5 mol % in allsilanes) of the compound 4 and 32.05 g of acetone were charged into a100 mL flask. While the resultant mixture solution was stirred with amagnetic stirrer, 6.57 g of a 0.01 mol/L hydrochloric acid was addeddropwise into the mixture solution. After the completion of theaddition, the flask was transferred into an oil bath adjusted to 85° C.,and under warming-reflux, the reaction was effected for 240 minutes.Then, the reaction solution was cooled down to room temperature and tothe reaction solution, 21 g of propylene glycol monomethyl ether acetatewas added. From the resultant reaction solution, ethanol as a reactionby-product, water, and hydrochloric acid were distilled off underreduced pressure and the resultant reaction mixture was concentrated toobtain a hydrolysis-condensation product (polymer) propylene glycolmonomethyl ether acetate solution. To the obtained solution, propyleneglycol monoethyl ether was added to adjust the resultant solution tocontain a solid residue in a proportion of 15% by weight at 140° C.while the solvent ratio of propylene glycol monomethyl etheracetatepropylene glycol monoethyl ether was 20/80. The obtained polymercorresponded to Formula (5-6) and had a weight average molecular weightmeasured by GPC of Mw 1,600 in terms of polystyrene.

Synthesis Example 7

15.12 g (75 mol % in all silanes) of tetraethoxysilane, 1.21 g (7 mol %in all silanes) of methyltriethoxysilane, 1.34 g (7 mol % in allsilanes) of phenyltrimethoxysilane, 1.69 g (6 mol % in all silanes) ofmethylsulfonyl methylphenyl trimethoxysilane, 2.03 g (5 mol % in allsilanes) of the compound 5 and 32.08 g of acetone were charged into a100 mL flask. While the resultant mixture solution was stirred with amagnetic stirrer, 6.53 g of a 0.01 mol/L hydrochloric acid was addeddropwise into the mixture solution. After the completion of theaddition, the flask was transferred into an oil bath adjusted to 85° C.,and under warming-reflux, the reaction was effected for 240 minutes.Then, the reaction solution was cooled down to room temperature and tothe reaction solution, 21 g of propylene glycol monomethyl ether acetatewas added. From the resultant reaction solution, ethanol as a reactionby-product, water, and hydrochloric acid were distilled off underreduced pressure and the resultant reaction mixture was concentrated toobtain a hydrolysis-condensation product (polymer) propylene glycolmonomethyl ether acetate solution. To the obtained solution, propyleneglycol monoethyl ether was added to adjust the resultant solution tocontain a solid residue in a proportion of 15% by weight at 140° C.while the solvent ratio of propylene glycol monomethyl etheracetatepropylene glycol monoethyl ether was 20/80. The obtained polymercorresponded to Formula (5-7) and had a weight average molecular weightmeasured by GPC of Mw 1,600 in terms of polystyrene.

Synthesis Example 8

15.66 g (75 mol % in all silanes) of tetraethoxysilane, 1.88 g (10.5 mol% in all silanes) of methyltriethoxysilane, 1.69 g (8.5 mol % in allsilanes) of phenyltrimethoxysilane, 1.65 g (5 mol % in all silanes) of(5-(triethoxysilyl)norbornene-2,3-dicarboxylic anhydride, 0.41 g (1 mol% in all silanes) of 3-(triethoxysilylpropyl)diallyl isocyanurate, and31.94 g of acetone were charged into a 100 mL flask. While the resultantmixture solution was stirred with a magnetic stirrer, 6.77 g of a 0.01mol/L hydrochloric acid was added dropwise into the mixture solution.After the completion of the addition, the flask was transferred into anoil bath adjusted to 85° C., and under warming-reflux, the reaction waseffected for 240 minutes. Then, the reaction solution was cooled down toroom temperature and to the reaction solution, 21 g of propylene glycolmonomethyl ether acetate was added. From the resultant reactionsolution, ethanol as a reaction by-product, water, and hydrochloric acidwere distilled off under reduced pressure and the resultant reactionmixture was concentrated to obtain a hydrolysis-condensation product(polymer) propylene glycol monomethyl ether acetate solution. To theobtained solution, propylene glycol monoethyl ether was added to adjustthe resultant solution to contain a solid residue in a proportion of 15%by weight at 140° C. while the solvent ratio of propylene glycolmonomethyl ether acetatepropylene glycol monoethyl ether was 20/80. Theobtained polymer corresponded to Formula (5-8) and had a weight averagemolecular weight measured by GPC of Mw 1,600 in terms of polystyrene.

Synthesis Example 9

15.37 g (75 mol % in all silanes) of tetraethoxysilane, 1.84 g (10.5 mol% in all silanes) of methyltriethoxysilane, 1.66 g (8.5 mol % in allsilanes) of phenyltrimethoxysilane, 2.07 g (5 mol % in all silanes) ofthe compound 5, 0.41 g (1 mol % in all silanes) of3-(triethoxysilylpropyl)diallyl isocyanurate, and 32.01 g of acetonewere charged into a 100 mL flask. While the resultant mixture solutionwas stirred with a magnetic stirrer, 6.64 g of a 0.01 mol/L hydrochloricacid was added dropwise into the mixture solution. After the completionof the addition, the flask was transferred into an oil bath adjusted to85° C., and under warming-reflux, the reaction was effected for 240minutes. Then, the reaction solution was cooled down to room temperatureand to the reaction solution, 21 g of propylene glycol monomethyl etheracetate was added. From the resultant reaction solution, ethanol as areaction by-product, water, and hydrochloric acid were distilled offunder reduced pressure and the resultant reaction mixture wasconcentrated to obtain a hydrolysis-condensation product (polymer)propylene glycol monomethyl ether acetate solution. To the obtainedsolution, propylene glycol monoethyl ether was added to adjust theresultant solution to contain a solid residue in a proportion of 15% byweight at 140° C. while the solvent ratio of propylene glycol monomethylether acetatepropylene glycol monoethyl ether was 20/80. The obtainedpolymer corresponded to Formula (5-9) and had a weight average molecularweight measured by GPC of Mw 1,600 in terms of polystyrene.

Synthesis Example 10

15.80 g (75 mol % in all silanes) of tetraethoxysilane, 1.80 g (10.0 mol% in all silanes) of methyltriethoxysilane, 2.01 g (10.0 mol % in allsilanes) of phenyltrimethoxysilane, 1.66 g (5 mol % in all silanes) of(5-(triethoxysilyl)norbornene-2,3-dicarboxylic anhydride, and 31.90 g ofacetone were charged into a 100 mL flask. While the resultant mixturesolution was stirred with a magnetic stirrer, 6.83 g of a 0.01 mol/Lhydrochloric acid was added dropwise into the mixture solution. Afterthe completion of the addition, the flask was transferred into an oilbath adjusted to 85° C., and under warming-reflux, the reaction waseffected for 240 minutes. Then, the reaction solution was cooled down toroom temperature and to the reaction solution, 21 g of propylene glycolmonomethyl ether acetate was added. From the resultant reactionsolution, ethanol as a reaction by-product, water, and hydrochloric acidwere distilled off under reduced pressure and the resultant reactionmixture was concentrated to obtain a hydrolysis-condensation product(polymer) propylene glycol monomethyl ether acetate solution. To theobtained solution, propylene glycol monoethyl ether was added to adjustthe resultant solution to contain a solid residue in a proportion of 15%by weight at 140° C. while the solvent ratio of propylene glycolmonomethyl ether acetatepropylene glycol monoethyl ether was 20/80. Theobtained polymer corresponded to Formula (5-10) and had a weight averagemolecular weight measured by GPC of Mw 1,600 in terms of polystyrene.

Synthesis Example 11

15.50 g (75 mol % in all silanes) of tetraethoxysilane, 1.77 g (10.0 mol% in all silanes) of methyltriethoxysilane, 1.97 g (10.0 mol % in allsilanes) of phenyltrimethoxysilane, 2.09 g (5 mol % in all silanes) ofthe compound 5, and 31.98 g of acetone were charged into a 100 mL flask.While the resultant mixture solution was stirred with a magneticstirrer, 6.70 g of a 0.01 mol/L hydrochloric acid was added dropwiseinto the mixture solution. After the completion of the addition, theflask was transferred into an oil bath adjusted to 85° C., and underwarming-reflux, the reaction was effected for 240 minutes. Then, thereaction solution was cooled down to room temperature and to thereaction solution, 21 g of propylene glycol monomethyl ether acetate wasadded. From the resultant reaction solution, ethanol as a reactionby-product, water, and hydrochloric acid were distilled off underreduced pressure and the resultant reaction mixture was concentrated toobtain a hydrolysis-condensation product (polymer) propylene glycolmonomethyl ether acetate solution. To the obtained solution, propyleneglycol monoethyl ether was added to adjust the resultant solution tocontain a solid residue in a proportion of 15% by weight at 140° C.while the solvent ratio of propylene glycol monomethyl etheracetatepropylene glycol monoethyl ether was 20/80. The obtained polymercorresponded to Formula (5-11) and had a weight average molecular weightmeasured by GPC of Mw 1,600 in terms of polystyrene.

Synthesis Example 12

15.17 g (75 mol % in all silanes) of tetraethoxysilane, 2.60 g (15 mol %in all silanes) of methyltriethoxysilane, 2.01 g (5 mol % in allsilanes) of 3-(triethoxysilylpropyl)diallyl isocyanurate, 1.59 g (5 mol% in all silanes) of 5-(triethoxysilyl)norbornene-2,3-dicarboxylicanhydride, and 32.06 g of acetone were charged into a 100 mL flask.While the resultant mixture solution was stirred with a magneticstirrer, 6.56 g of a 0.01 mol/L hydrochloric acid was added dropwiseinto the mixture solution. After the completion of the addition, theflask was transferred into an oil bath adjusted to 85° C., and underwarming-reflux, the reaction was effected for 240 minutes. Then, thereaction solution was cooled down to room temperature and to thereaction solution, 21 g of propylene glycol monomethyl ether acetate wasadded. From the resultant reaction solution, ethanol as a reactionby-product, water, and hydrochloric acid were distilled off underreduced pressure and the resultant reaction mixture was concentrated toobtain a hydrolysis-condensation product (polymer) propylene glycolmonomethyl ether acetate solution. To the obtained solution, propyleneglycol monoethyl ether was added to adjust the resultant solution tocontain a solid residue in a proportion of 15% by weight at 140° C.while the solvent ratio of propylene glycol monomethyl etheracetatepropylene glycol monoethyl ether was 20/80. The obtained polymerof Formula (5-12) had a weight average molecular weight measured by GPCof Mw 1,600 in terms of polystyrene.

Synthesis Example 13

14.90 g (75 mol % in all silanes) of tetraethoxysilane, 2.55 g (15 mol %in all silanes) of methyltriethoxysilane, 1.97 g (5 mol % in allsilanes) of 3-(triethoxysilylpropyl)diallyl isocyanurate, 2.01 g (5 mol% in all silanes) of the compound 5, and 32.13 g of acetone were chargedinto a 100 mL flask. While the resultant mixture solution was stirredwith a magnetic stirrer, 6.44 g of a 0.01 mol/L hydrochloric acid wasadded dropwise into the mixture solution. After the completion of theaddition, the flask was transferred into an oil bath adjusted to 85° C.,and under warming-reflux, the reaction was effected for 240 minutes.Then, the reaction solution was cooled down to room temperature and tothe reaction solution, 21 g of propylene glycol monomethyl ether acetatewas added. From the resultant reaction solution, ethanol as a reactionby-product, water, and hydrochloric acid were distilled off underreduced pressure and the resultant reaction mixture was concentrated toobtain a hydrolysis-condensation product (polymer) propylene glycolmonomethyl ether acetate solution. To the obtained solution, propyleneglycol monoethyl ether was added to adjust the resultant solution tocontain a solid residue in a proportion of 15% by weight at 140° C.while the solvent ratio of propylene glycol monomethyl etheracetatepropylene glycol monoethyl ether was 20/80. The obtained polymerof Formula (5-13) had a weight average molecular weight measured by GPCof Mw 1,600 in terms of polystyrene.

Synthesis Example 14

15.89 g (75 mol % in all silanes) of tetraethoxysilane, 2.18 g (12 mol %in all silanes) of methyltriethoxysilane, 1.41 g (7 mol % in allsilanes) of phenyltrimethoxysilane, 1.77 g (6 mol % in all silanes) ofmethylsulfonyl methylphenyl trimethoxysilane, and 31.88 g of acetonewere charged into a 100 mL flask. While the resultant mixture solutionwas stirred with a magnetic stirrer, 6.88 g of a 0.01 mol/L hydrochloricacid was added dropwise into the mixture solution. After the completionof the addition, the flask was transferred into an oil bath adjusted to85° C., and under warming-reflux, the reaction was effected for 240minutes. Then, the reaction solution was cooled down to room temperatureand to the reaction solution, 21 g of propylene glycol monomethyl etheracetate was added. From the resultant reaction solution, ethanol as areaction by-product, water, and hydrochloric acid were distilled offunder reduced pressure and the resultant reaction mixture wasconcentrated to obtain a hydrolysis-condensation product (polymer)propylene glycol monomethyl ether acetate solution. To the obtainedsolution, propylene glycol monoethyl ether was added to adjust theresultant solution to contain a solid residue in a proportion of 15% byweight at 140° C. while the solvent ratio of propylene glycol monomethylether acetatepropylene glycol monoethyl ether was 20/80. The obtainedpolymer of Formula (E-1) had a weight average molecular weight measuredby GPC of Mw 1,600 in terms of polystyrene.

Comparative Synthesis Example 1

4.30 g (20 mol % in all silanes) of tetraethoxysilane, 3.68 g (20 mol %in all silanes) of methyltriethoxysilane, 10.24 g (50 mol % in allsilanes) of phenyltrimethoxysilane, 3.39 g (10 mol % in all silanes) of(5-(triethoxysilyl)norbornene-2,3-dicarboxylic anhydride, and 32.43 g ofacetone were charged into a 100 mL flask. While the reaction mixturesolution was stirred with a magnetic stirrer, 5.96 g of a 0.01 mol/Lhydrochloric acid was added dropwise into the mixture solution. Afterthe completion of the addition, the flask was transferred into an oilbath adjusted to 85° C., and under warming-reflux, the reaction waseffected for 240 minutes. Then, the reaction solution was cooled down toroom temperature and to the reaction solution, 21 g of propylene glycolmonomethyl ether acetate was added. From the resultant reactionsolution, ethanol as a reaction by-product, water, and hydrochloric acidwere distilled off under reduced pressure and the resultant reactionmixture was concentrated to obtain a hydrolysis-condensation product(polymer) propylene glycol monomethyl ether acetate solution. To theobtained solution, propylene glycol monoethyl ether was added to adjustthe resultant solution to contain a solid residue in a proportion of 15%by weight at 140° C. while the solvent ratio of propylene glycolmonomethyl ether acetatepropylene glycol monoethyl ether was 20/80. Theobtained polymer of Formula (E-2) had a weight average molecular weightmeasured by GPC of Mw 800 in terms of polystyrene.

Comparative Synthesis Example 2

4.37 g (20 mol % in all silanes) of tetraethoxysilane, 3.74 g (20 mol %in all silanes) of methyltriethoxysilane, 10.41 g (50 mol % in allsilanes) of phenyltrimethoxysilane, 3.05 g (10 mol % in all silanes) ofmethylsulfonyl methylphenyl trimethoxysilane, and 32.37 g of acetonewere charged into a 100 mL flask. While the resultant mixture solutionwas stirred with a magnetic stirrer, 6.05 g of a 0.01 mol/L hydrochloricacid was added dropwise into the mixture solution. After the completionof the addition, the flask was transferred into an oil bath adjusted to85° C., and under warming-reflux, the reaction was effected for 240minutes. Then, the reaction solution was cooled down to room temperatureand to the reaction solution, 21 g of propylene glycol monomethyl etheracetate was added. From the resultant reaction solution, ethanol as areaction by-product, water, and hydrochloric acid were distilled offunder reduced pressure and the resultant reaction mixture wasconcentrated to obtain a hydrolysis-condensation product (polymer)propylene glycol monomethyl ether acetate solution. To the obtainedsolution, propylene glycol monoethyl ether was added to adjust theresultant solution to contain a solid residue in a proportion of 15% byweight at 140° C. while the solvent ratio of propylene glycol monomethylether acetatepropylene glycol monoethyl ether was 20/80. The obtainedpolymer of Formula (E-3) had a weight average molecular weight measuredby GPC of Mw 1,000 in terms of polystyrene.

Comparative Synthesis Example 3

4.15 g (20 mol % in all silanes) of tetraethoxysilane, 3.55 g (20 mol %in all silanes) of methyltriethoxysilane, 9.88 g (50 mol % in allsilanes) of phenyltrimethoxysilane, 4.12 g (10 mol % in all silanes) of3-(triethoxysilylpropyl)diallyl isocyanurate, and 32.55 g of acetonewere charged into a 100 mL flask. While the resultant mixture solutionwas stirred with a magnetic stirrer, 5.75 g of a 0.01 mol/L hydrochloricacid was added dropwise into the mixture solution. After the completionof the addition, the flask was transferred into an oil bath adjusted to85° C., and under warming-reflux, the reaction was effected for 240minutes. Then, the reaction solution was cooled down to room temperatureand to the reaction solution, 21 g of propylene glycol monomethyl etheracetate was added. From the resultant reaction solution, ethanol as areaction by-product, water, and hydrochloric acid were distilled offunder reduced pressure and the resultant reaction mixture wasconcentrated to obtain a hydrolysis-condensation product (polymer)propylene glycol monomethyl ether acetate solution. To the obtainedsolution, propylene glycol monoethyl ether was added to adjust theresultant solution to contain a solid residue in a proportion of 15% byweight at 140° C. while the solvent ratio of propylene glycol monomethylether acetatepropylene glycol monoethyl ether was 20/80. The obtainedpolymer of Formula (E-4) had a weight average molecular weight measuredby GPC of Mw 1,000 in terms of polystyrene.

Comparative Synthesis Example 4

4.34 g (20 mol % in all silanes) of tetraethoxysilane, 3.71 g (20 mol %in all silanes) of methyltriethoxysilane, 10.32 g (50 mol % in allsilanes) of phenyltrimethoxysilane, 1.51 g (5 mol % in all silanes) ofmethylsulfonyl methylphenyl trimethoxysilane, 1.71 g (5 mol % in allsilanes) of (5-(triethoxysilyl)norbornene-2,3-dicarboxylic anhydride,and 32.40 g of acetone were charged into a 100 mL flask. While theresultant mixture solution was stirred with a magnetic stirrer, 6.00 gof a 0.01 mol/L hydrochloric acid was added dropwise into the mixturesolution. After the completion of the addition, the flask wastransferred into an oil bath adjusted to 85° C., and underwarming-reflux, the reaction was effected for 240 minutes. Then, thereaction solution was cooled down to room temperature and to thereaction solution, 21 g of propylene glycol monomethyl ether acetate wasadded. From the resultant reaction solution, ethanol as a reactionby-product, water, and hydrochloric acid were distilled off underreduced pressure and the resultant reaction mixture was concentrated toobtain a hydrolysis-condensation product (polymer) propylene glycolmonomethyl ether acetate solution. To the obtained solution, propyleneglycol monoethyl ether was added to adjust the resultant solution tocontain a solid residue in a proportion of 15% by weight at 140° C.while the solvent ratio of propylene glycol monomethyl etheracetatepropylene glycol monoethyl ether was 20/80. The obtained polymerof Formula (E-5) had a weight average molecular weight measured by GPCof Mw 900 in terms of polystyrene.

Preparation of Resist Underlayer Film

The silicon-containing polymers obtained in Synthesis Examples 1 to 14and Comparative Synthesis Examples 1 to 4 were each blended with anacid, a curing catalyst, an additive, a solvent, and water in ratiosshown in Table 1. The resultant blend was filtered with a 0.1 urnfluorinated resin filter to prepare each of the solutions of the resistunderlayer film forming compositions.

In Table 1 and Table 2, maleic acid is abbreviated as MA;(3-triethoxysilylpropyl)-4,5-dihydroimidazole is abbreviated asIMIDTEOS; triphenylsulfonium trifluoromethanesulfonate is abbreviated asTPS105; monotriphenylsulfonium maleate is abbreviated as TPSMA;triphenylsulfonium camphorsulfonate is abbreviated as TPSCS;(5-(triethoxysilyl)norbornene-2,3-dicarboxylic anhydride is abbreviatedas NorAnTEOS; propylene glycol monomethyl ether acetate is abbreviatedas PGMEA; and propylene glycol monoethyl ether is abbreviated as PGEE.As the water, ultrapure water was used. Each blending amount isexpressed in parts by mass. The blending ratio of the polymer isindicated not as the mass of the polymer solution, but as the mass ofthe polymer itself.

TABLE 1 Curing Polymer Acid catalyst Additive Solvent Water Example 1Synthesis MA IMIDTEOS PGMEA PGEE Water (parts by mass) Example 1 0.020.006 7 80 13 2 Example 2 Synthesis MA IMIDTEOS PGMEA PGEE Water (partsby mass) Example 2 0.02 0.006 7 80 13 2 Example 3 Synthesis MA IMIDTEOSPGMEA PGEE Water (parts by mass) Example 3 0.02 0.006 7 80 13 2 Example4 Synthesis MA IMIDTEOS PGMEA PGEE Water (parts by mass) Example 4 0.020.006 7 80 13 2 Example 5 Synthesis MA IMIDTEOS PGMEA PGEE Water (partsby mass) Example 5 0.02 0.006 7 80 13 2 Example 6 Synthesis MA IMIDTEOSPGMEA PGEE Water (parts by mass) Example 6 0.02 0.006 7 80 13 2 Example7 Synthesis MA IMIDTEOS PGMEA PGEE Water (parts by mass) Example 7 0.020.006 7 80 13 2 Example 8 Synthesis MA IMIDTEOS PGMEA PGEE Water (partsby mass) Example 8 0.02 0.006 7 80 13 2 Example 9 Synthesis MA IMIDTEOSPGMEA PGEE Water (parts by mass) Example 9 0.02 0.006 7 80 13 2 Example10 Synthesis MA IMIDTEOS PGMEA PGEE Water (parts by mass) Example 100.02 0.006 7 80 13 2 Example 11 Synthesis MA IMIDTEOS PGMEA PGEE Water(parts by mass) Example 11 0.02 0.006 7 80 13 2 Example 12 Synthesis MAIMIDTEOS PGMEA PGEE Water (parts by mass) Example 12 0.02 0.006 7 80 132 Example 13 Synthesis MA IMIDTEOS PGMEA PGEE Water (parts by mass)Example 13 0.02 0.006 7 80 13 2 Example 14 Synthesis MA IMIDTEOSNorAnTEOS PGMEA PGEE Water (parts by mass) Example 14 0.02 0.006 0.10 780 13 2 Example 15 Synthesis MA IMIDTEOS Compound 5 PGMEA PGEE Water(parts by mass) Example 14 0.06 0.012 0.10 7 80 13 2

TABLE 2 Curing Polymer Acid catalyst Additive Solvent Water Example 16Synthesis MA TPSMA PGMEA PGEE Water (parts by mass) Example 1 0.02 0.0067 80 13 2 Example 17 Synthesis MA TPS105 PGMEA PGEE Water (parts bymass) Example 1 0.02 0.006 7 80 13 2 Example 18 Synthesis MA TPSCS PGMEAPGEE Water (parts by mass) Example 1 0.02 0.006 7 80 13 2 Example 19Synthesis MA IMIDTEOS TPS105 PGMEA PGEE Water (parts by mass) Example 10.02 0.006 0.02 7 80 13 2 Example 20 Synthesis MA IMIDTEOS TPSCS PGMEAPGEE Water (parts by mass) Example 1 0.02 0.006 0.02 7 80 13 2 Example21 Synthesis MA TPSMA TPS105 PGMEA PGEE Water (parts by mass) Example 10.02 0.02  0.02 7 80 13 2 Example 22 Synthesis MA TPSMA TPSCS PGMEA PGEEWater (parts by mass) Example 1 0.02 0.02  0.02 7 80 13 2 ComparativeComparative MA IMIDTEOS PGMEA PGEE Water Example 1 Synthesis 0.02 0.0067 80 13 (parts by mass) Example 1 2 Comparative Comparative MA IMIDTEOSPGMEA PGEE Water Example 2 Synthesis 0.02 0.006 7 80 13 (parts by mass)Example 2 2 Comparative Comparative MA IMIDTEOS PGMEA PGEE Water Example3 Synthesis 0.02 0.006 7 80 13 (parts by mass) Example 3 2 ComparativeComparative MA IMIDTEOS PGMEA PGEE Water Example 4 Synthesis 0.02 0.0067 80 13 (parts by mass) Example 4 2

(Measurement of Optical Constants)

The Si-containing resist underlayer film forming compositions preparedin Examples 1 to 22 and Comparative Examples 1 to 4 were each appliedonto corresponding silicon wafers using a spinner. The composition washeated on a hot plate at 200° C. for 1 minute to form a Si-containingresist underlayer film (film thickness: 0.05 m). Then, the refractiveindex (n value) and the optical absorptivity (k value; also called theattenuation coefficient) of the resist underlayer film at a wavelengthof 193 nm were measured using a spectro-ellipsometer (VUV-VASE VU-302;manufactured by J.A. Woollam Co., Inc.).

(Measurement of Dry Etching Rate)

Etchers and etching gases used in the measurement of dry etching rateswere as follows:

ES401 (manufactured by Nippon Scientific Co., Ltd.): CF₄RIE-10NR (manufactured by Samco, Inc.): O₂.

The solutions of the Si-containing resist underlayer film formingcompositions prepared in Examples 1 to 22 and Comparative Examples 1 to4 were each applied onto corresponding silicon wafers using a spinner.The solution was heated on a hot plate at 240° C. for 1 minute to formSi-containing resist underlayer films (film thickness: 0.08 μm (formeasurement of etching rate with CF₄ gas), and 0.05 μm (for measurementof etching rate with O₂ gas)). In a similar manner, organic underlayerfilm forming compositions were each applied onto corresponding siliconwafers using a spinner to form coating films (film thickness: 0.20 μm)thereon. By using O₂ gas as the etching gas, the dry etching rate of theorganic underlayer film was measured, and compared with the dry etchingrates of the Si-containing resist underlayer films of Examples 1 to 22and Comparative Examples 1 to 4.

Etching rate with Refractive Optical fluorine-based Oxygen-based TABLE 3index absorptivity gas gas resistance Example 1 1.64 0.27 23 0.03Example 2 1.64 0.28 23 0.03 Example 3 1.64 0.27 23 0.03 Example 4 1.630.27 23 0.03 Example 5 1.65 0.28 23 0.04 Example 6 1.64 0.27 24 0.04Example 7 1.63 0.28 24 0.04 Example 8 1.70 0.18 24 0.03 Example 9 1.690.19 25 0.03 Example 10 1.70 0.20 23 0.03 Example 11 1.71 0.21 23 0.03Example 12 1.67 0.08 23 0.03 Example 13 1.67 0.09 24 0.03 Example 141.64 0.27 23 0.03 Example 15 1.65 0.28 23 0.03

TABLE 4 Etching rate with Oxygen- Refractive Optical fluorine-basedbased gas index absorptivity gas resistance Example 16 1.63 0.28 23 0.03Example 17 1.63 0.27 24 0.03 Example 18 1.63 0.28 23 0.03 Example 191.63 0.28 23 0.03 Example 10 1.63 0.28 23 0.03 Example 21 1.62 0.29 230.03 Example 22 1.62 0.29 23 0.03 Comparative 1.85 0.71 21 0.05 Example1 Comparative 1.80 0.81 22 0.05 Example 2 Comparative 1.92 0.76 23 0.06Example 3 Comparative 1.83 0.76 22 0.05 Example 4

(Preparation of Organic Resist Underlayer Film A)

In nitrogen, into a 100 mL four-neck flask, carbazole (6.69 g, 0.040mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone(7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.),and p-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufacturedby Tokyo Chemical Industry Co., Ltd.) were charged and thereto,1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Inc.) wasadded, followed by stirring the resultant mixture. The temperature ofthe reaction mixture was elevated to 100° C. to dissolve the mixture andthe polymerization was initiated. After 24 hours, the reaction mixturewas left to be cooled down to 60° C., and then, to the reaction mixture,chloroform (34 g, manufactured by Kanto Chemical Co., Inc.) was added todilute the reaction mixture, followed by reprecipitating the resultantreaction mixture in methanol (168 g, manufactured by Kanto Chemical Co.,Inc.). The obtained precipitate was filtered and was dried using avacuum drier at 80° C. for 24 hours to obtain 9.37 g of the objectivepolymer (Formula (E-6), hereinafter abbreviated as PCzFL).

The measurement result of ¹H-NMR of PCzFL was as follows:

¹H-NMR (400 MHz, DMSO-d₆): δ7.03-7.55 (br, 12H), δ7.61-8.10 (br, 4H),δ11.18 (br, 1H).

The weight average molecular weight Mw of PCzFL measured by GPC in termsof polystyrene was 2,800 and a polydispersity Mw/Mn was 1.77.

With 20 g of the obtained resin, 3.0 g of tetramethoxymethyl glycoluril(trade name: POWDER LINK 1174; manufactured by Mitsui Cytec Ltd.) as acrosslinker, 0.30 g of pyridinium p-toluenesulfonate as a catalyst, and0.06 g of MEGAFAC R-30 (trade name; manufactured by Dainippon Ink &Chemicals Inc.) as a surfactant were mixed. The resultant mixture wasdissolved in 88 g of propylene glycol monomethyl ether acetate toprepare a solution. The solution was then filtered using a polyethylenemicrofilter having a pore diameter of 0.10 μm and was further filteredusing a polyethylene microfilter having a pore diameter of 0.05 μm toprepare a solution of an organic resist underlayer film formingcomposition to be used for a lithography process for a multilayer film.

(Resist Patterning Evaluation: Evaluation Through NTD Process in whichDevelopment is Performed with Organic Solvent)

The organic underlayer film (layer A) forming composition obtained abovewas applied onto a silicon wafer, and the composition was baked on a hotplate at 240° C. for 60 seconds to obtain an organic underlayer film(layer A) having a film thickness of 200 nm. The Si-containing resistunderlayer film (layer B) forming compositions obtained in Examples 1 to11 and 14 to 22 and Comparative Examples 1 to 4 were each applied ontothe corresponding organic underlayer films (layers A). The compositionwas baked on a hot plate at 240° C. for 60 seconds to obtain aSi-containing resist underlayer film (layer B). The Si-containing resistunderlayer films (layers B) had a film thickness of 35 nm.

Onto each of the layers B, a commercially available photoresist solution(trade name: FAiRS-9521NT05; manufactured by FUJIFILM Corporation) wasapplied by a spinner and the solution was heated on a hot plate at 100°C. for 1 minute to form photoresist films (layers C) having a filmthickness of 85 nm.

Using an NSR-S307E scanner manufactured by Nikon Corporation(wavelength: 193 nm, NA, σ: 0.85, 0.93/0.85), exposure was performedthrough a mask set to form a photoresist after the development having aline width and a width between lines of 0.060 μm each, that is, 0.060-μmdense line and space (L/S)=1/2, and through a mask set to form aphotoresist after the development having a line width and a widthbetween lines of 0.058 μm each, that is, 0.058-μm dense line and space(L/S) 1/1. Then, the resist pattern was baked on a hot plate at 100° C.for 60 seconds, was cooled down, and was developed using butyl acetate(solvent developer) for 60 seconds to form a negative-type pattern onthe resist underlayer film (layer B). With respect to the obtainedphotoresist patterns, a photoresist pattern in which no large patternpeeling, no undercut, or no widening (footing) at a line bottom occurredwas evaluated as favorable.

In Table 5 and Table 6, the results of observing a skirt shape of theresist after the lithography evaluation are shown.

TABLE 5 Width and Interval Width and Interval in Pattern in Pattern 1/11/2 Example 1 Favorable Favorable Example 2 Favorable Favorable Example3 Favorable Favorable (partial peeling) Example 4 Favorable Favorable(partial peeling) Example 5 Favorable Favorable (partial peeling)Example 6 Favorable Favorable (partial peeling) Example 7 FavorableFavorable Example 8 Favorable Favorable Example 9 Favorable FavorableExample 10 Favorable Favorable Example 11 Favorable Favorable Example 14Favorable Favorable Example 15 Favorable Favorable

TABLE 6 Width and Interval Width and Interval in Pattern in Pattern 1/11/2 Example 16 Favorable Favorable Example 17 Favorable FavorableExample 18 Favorable Favorable Example 19 Favorable Favorable Example 20Favorable Favorable Example 21 Favorable Favorable Example 22 FavorableFavorable Comparative Failed (large peeling) Failed (large peeling)Example 1 Comparative Failed (large peeling) Failed (large peeling)Example 2 Comparative Failed (large peeling) Failed (large peeling)Example 3 Comparative Failed (large peeling) Failed (large peeling)Example 4

(Resist Patterning Evaluation: Evaluation Via PTD Process of PerformingDevelopment with Alkaline Developer)

The organic underlayer film (layer A) forming composition obtained asdescribed above was applied onto a silicon wafer, and the appliedcomposition was baked on a hot plate at 240° C. for 60 seconds to obtainan organic underlayer film (layer A) having a film thickness of 200 am.The Si-containing resist underlayer film (layer B) forming compositionsobtained in Examples 12 and 13 and Comparative Examples 1 to 4 were eachapplied onto the corresponding organic underlayer films (layers A). Theapplied composition was baked on a hot plate at 240° C. for 60 secondsto obtain a Si-containing resist underlayer film (layer B). TheSi-containing resist underlayer films (layers B) had a film thickness of35 nm. Onto each of the layers B, a commercially available photoresistsolution (trade name: AR 2772; manufactured by JSR Corporation) wasapplied by a spinner, and the applied solution was baked on a hot plateat 110° C. for 60 seconds to form a photoresist film (layer C) having afilm thickness of 120 nm. The patterning of the resist was performedusing an ArF exposing machine S-307E, manufactured by Nikon Corporation(wavelength: 193 nm, NA, σ: 0.85, 0.93/0.85 (Dipole), immersion liquid:water). The target was a photoresist after the development having a linewidth and a width between lines of 0.065 pin each, which is what iscalled lines and spaces (dense lines), and the exposure was performedthrough a mask set to form such a photoresist.

Then, the resultant product was baked on a hot plate at 110° C. for 60seconds, was cooled down, and was developed with a tetramethylammoniumhydroxide aqueous solution (developer) having a concentration of 2.38%by mass in a 60-second single paddle process. With respect to theobtained photoresist patterns, a photoresist pattern in which no largepattern peeling, no undercut, or no widening (footing) at a line bottomoccurred was evaluated as favorable.

In Table 7, a result of observing a skirt shape of the resist after thelithography evaluation is shown.

TABLE 7 Example 12 Favorable Example 13 Favorable Comparative Example 1Failed (large peeling) Comparative Example 2 Failed (large peeling)Comparative Example 3 Failed (large peeling) Comparative Example 4Failed (large peeling)

INDUSTRIAL APPLICABILITY

A resist underlayer film forming composition for lithography usable forthe production of semiconductor devices is provided. A resist underlayerfilm forming composition for lithography for forming a resist underlayerfilm usable as a hardmask is provided. A resist underlayer film formingcomposition for lithography for forming a resist underlayer film usableas an anti-reflective coating is provided.

1. A resist underlayer film forming composition for lithography,comprising: as a silane, a hydrolyzable silane, a hydrolysis productthereof, or a hydrolysis-condensation product thereof, wherein thehydrolyzable silane includes a hydrolyzable silane of Formula (1) or ahydrolyzable silane containing a combination of a hydrolyzable silane ofFormula (1) with a hydrolyzable silane of Formula (2), and a content ofthe hydrolyzable silane of Formula (1) or the hydrolyzable silanecontaining a combination of a hydrolyzable silane of Formula (1) with ahydrolyzable silane of Formula (2) in all silanes is less than 50% bymole,R¹ _(a)R² _(b)Si(R³)_(4−(a+b))  Formula (1) [in Formula (1), R¹ is amonovalent organic group containing a group of Formula (1-1), Formula(1-2), Formula (1-3), Formula (1-4), or Formula (1-5):

(in Formula (1-1), Formula (1-2), Formula (1-3), Formula (1-4), andFormula (1-5), each of T¹, T⁴, and T⁷ is an alkylene group, a cyclicalkylene group, an alkenylene group, an arylene group, a sulfur atom, anoxygen atom, an oxycarbonyl group, an amido group, a secondary aminogroup, or a combination of these groups and atoms; T² is an alkyl group;each of T³ and T⁵ is an aliphatic ring or an aromatic ring; each of T⁶and T⁸ is a lactone ring; and n is an integer of 1 or 2) and is bondedto a silicon atom through a Si—C bond; R² is an alkyl group, an arylgroup, a halogenated alkyl group, a halogenated aryl group, an alkenylgroup, or an organic group having an epoxy group, an acryloyl group, amethacryloyl group, a mercapto group, an amino group, or a cyano group,and is bonded to a silicon atom through a Si—C bond; R³ is an alkoxygroup, an acyloxy group, or a halogen group; and a is an integer of 1, bis an integer of 0 or 1, and a+b is an integer of 1 or 2],R⁴ _(a1)R⁵ _(b1)Si(R⁶)_(4−(a1+b1))  Formula (2) [in Formula (2), R⁴ is amonovalent organic group containing a group of Formula (2-1), Formula(2-2), or Formula (2-3):

and is bonded to a silicon atom through a Si—C bond; R⁵ is an alkylgroup, an aryl group, a halogenated alkyl group, a halogenated arylgroup, an alkenyl group, or an organic group having an epoxy group, anacryloyl group, a methacryloyl group, a mercapto group, an amino group,or a cyano group, and is bonded to a silicon atom through a Si—C bond;R⁶ is an alkoxy group, an acyloxy group, or a halogen group; and a₁ isan integer of 1, b₁ is an integer of 0 or 1, and a₁+b₁ is an integer of1 or 2].
 2. The resist underlayer film forming composition according toclaim 1, wherein a content of the hydrolyzable silane of Formula (1) orthe hydrolyzable silane containing a combination of a hydrolyzablesilane of Formula (1) with a hydrolyzable silane of Formula (2) in allsilanes is 5 to 45% by mole.
 3. The resist underlayer film formingcomposition according to claim 1, wherein a hydrolyzable silane ofFormula (2) is a hydrolyzable silane in which R⁴ is an organic groupcontaining a group of Formula (2-1), a hydrolyzable silane in which R⁴is an organic group containing a group of Formula (2-2), a hydrolyzablesilane in which R⁴ is an organic group containing a group of Formula(2-3), or a mixture of these hydrolyzable silanes.
 4. The resistunderlayer film forming composition according to claim 1, wherein ahydrolyzable silane containing a combination of a hydrolyzable silane ofFormula (1) with a hydrolyzable silane of Formula (2) contains ahydrolyzable silane of Formula (1) and a hydrolyzable silane of Formula(2) in a molar ratio of 1:0.01 to
 10. 5. The resist underlayer filmforming composition for lithography according to claim 1, wherein thehydrolyzable silane contains a hydrolyzable silane of Formula (1) or ahydrolyzable silane containing a combination of a hydrolyzable silane ofFormula (1) with a hydrolyzable silane of Formula (2), and anotherhydrolyzable silane, and the other hydrolyzable silane is at least oneorganic silicon compound selected from the group consisting of acompound of Formula (3):R⁷ _(a2)Si(R⁸)_(4−a2)  Formula (3) (in Formula (3), R⁷ is an alkylgroup, an aryl group, a halogenated alkyl group, a halogenated arylgroup, an alkenyl group, or an organic group having an epoxy group, anacryloyl group, a methacryloyl group, a mercapto group, or a cyanogroup, and is bonded to a silicon atom through a Si—C bond; R⁸ is analkoxy group, an acyloxy group, or a halogen group; and a₂ is an integerof 0 to 3) and a compound of Formula (4):[R⁹ _(c)Si(R¹⁰)_(3−c)]₂Y_(b2)  Formula (4) (in Formula (4), R⁹ is analkyl group and is bonded to a silicon atom through a Si—C bond; R¹⁰ isan alkoxy group, an acyloxy group, or a halogen group; Y is an alkylenegroup or an arylene group; b₂ is an integer of 0 or 1; and c is aninteger of 0 or 1).
 6. A resist underlayer film forming compositioncomprising: a hydrolysis product of a hydrolyzable silane of Formula (1)or the hydrolyzable silane containing a combination of a hydrolyzablesilane of Formula (1) with a hydrolyzable silane of Formula (2) in allsilanes is either 5 to 45% mole or in a molar ratio of 1:0.01 to 10, anda hydrolyzable silane of Formula (3) as claimed in claim 5, as apolymer.
 7. The resist underlayer film forming composition according toclaim 1, further comprising an acid as a hydrolysis catalyst.
 8. Theresist underlayer film forming composition according to claim 1, furthercomprising water.
 9. A resist underlayer film obtained by applying theresist underlayer film forming composition as claimed in claim 1 onto asemiconductor substrate, and baking the composition.
 10. A method forproducing a semiconductor device, the method comprising: applying theresist underlayer film forming composition as claimed in claim 1 onto asemiconductor substrate and baking the composition to form a resistunderlayer film; applying a composition for a resist onto the underlayerfilm to form a resist film; exposing the resist film to light;developing the resist after the exposure to obtain a resist pattern;etching the resist underlayer film using the resist pattern; andprocessing the semiconductor substrate using the patterned resist andthe patterned resist underlayer film.
 11. A method for producing asemiconductor device, the method comprising: forming an organicunderlayer film on a semiconductor substrate; applying the resistunderlayer film forming composition as claimed in claim 1, onto theorganic underlayer film and baking the composition to form a resistunderlayer film; applying a composition for a resist onto the resistunderlayer film to form a resist film; exposing the resist film tolight; developing the resist after the exposure to obtain a resistpattern; etching the resist underlayer film using the resist pattern;etching the organic underlayer film using the patterned resistunderlayer film; and processing the semiconductor substrate using thepatterned organic underlayer film.